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CN108027558A - For addition process manufacture liquid, mix can ultraviolet/visible light radiation curable resin composition - Google Patents

For addition process manufacture liquid, mix can ultraviolet/visible light radiation curable resin composition Download PDF

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Publication number
CN108027558A
CN108027558A CN201680056323.XA CN201680056323A CN108027558A CN 108027558 A CN108027558 A CN 108027558A CN 201680056323 A CN201680056323 A CN 201680056323A CN 108027558 A CN108027558 A CN 108027558A
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China
Prior art keywords
ultraviolet
addition process
weight
visible light
radiation
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CN201680056323.XA
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CN108027558B (en
Inventor
卢克·科威斯尼克
李泰彦
约翰·弗朗兹·格拉迪·安东尼厄斯·詹森
贝蒂·库森斯
任康太
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Stratasys Inc
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DSM IP Assets BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
    • B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Mechanical Engineering (AREA)
  • Polymerisation Methods In General (AREA)
  • Epoxy Resins (AREA)

Abstract

This document describes thermoset composition, hybrid polymer when it is suitable for being handled by using the addition process manufacturing equipment of the actinic radiation sources in ultraviolet and/or visible region with peak value spectral intensity, it contains light-initiated bag, the component of the component of cationically curable, free-radical curable and optional one or more additives.This thermoset composition contains Norrish I type photoinitiators; the Norrish I type photoinitiators are the compounds of the alkyl with the 14th race's atom, aryl or acyl group substitution, and/or have the ionization potential value of specified range relative to its known triplet.Also disclose by using the addition process manufacturing process of the actinic radiation sources with peak value spectral intensity in ultraviolet and/or visible region to produce the method for three dimensional articles, wherein using thermoset composition claimed.There is also described herein by its cured product.

Description

For addition process manufacture liquid, mix can ultraviolet/visible light radiation curing resin Composition
Technical field
The present invention relates to mix curing thermoset composition for addition process manufacturing process.
Cross reference to related applications
The priority of the U.S. Provisional Application No.62/235608 submitted this application claims on October 1st, 2015, its whole Content is incorporated herein by reference, as illustrating completely herein.
Background technology
Addition process manufacturing process for manufacturing three-dimensional body is well-known.Addition process manufacture utilizes the calculating of object Machine Computer Aided Design (CAD) data build three dimensional articles.These three dimensional articles can be by liquid resin, powder or other materials system Into.
The known of addition process manufacturing process, non-limiting examples are stereolithography (SL).Stereolithography is one Kind is used for the known method of the production product in quick modeling, prototype, pattern and some applications.SL uses the CAD of object Data, the wherein data are converted into the thin cross section of three-dimensional body.These data load in a computer, computer control Liquid radiation-curable resin composition that laser is received through in bucket scans cross sectional pattern, makes corresponding with cross section Resin thin layer cure.Cured layer, another cross section of laser scanning, so as to make at the top of preceding layer are coated with resin Another resin bed hardens.The process is repeated layer by layer until completing three-dimensional body.When originally forming, the three-dimensional body is usually not It is fully cured, it is referred to as " green compact model (green model) ".Although being not required, after green compact model can be subjected to Cure to strengthen the mechanical performance of finished product product.Such as the example of SL techniques is described in United States Patent (USP) 4,575,330.
Traditionally, laser serves as selected radiation source in addition process manufacturing process (such as stereolithography).Make With gas laser come to cure liquid radiation-curable resin composition be known.Laser energy in stereolithography system Transmission can be continuous wave (CW) or Q-switched pulse.CW lasers provide continuous laser energy, available for high-velocity scanning side In method.In history, the wavelength tradition of the laser of several types, the wherein output of peak value spectrum is used in stereolithography On in the range of 193nm to 355nm, but there is also other wavelength variations.The light that laser is sent is monochromatic, i.e. non- Occurs total spectrum output of high percentage in often narrow wave-length coverage.In the industry in the addition process manufacture system based on laser, Those to work under the peak value spectrum output of 355nm have become the most universal.
However, the system based on laser, particularly work under 355nm or peak value spectrum output close to 355nm that A little systems are not without shortcoming.A large amount of power outputs of this system based on laser produce excessively in exposure spots sometimes Heat, this may be harmful to resin.In addition, the point by point scanning on resin surface is required for using the laser of any wavelength, When wanting cured cross sectional pattern complicated, this process may especially take.In addition, the system price based on 355nm laser Costliness, and maintenance cost is high, high energy consumption.
Have begun to utilize with some relevant shortcomings of the system based on laser, other addition process manufacture systems to overcome Image projection technology (image projection technology) is used as actinic radiation sources.One of example is liquid crystal Show device (LCD), this technology is known in other industry (such as television set and computer monitor manufacture).Another non-limit Property example processed is the digital light processing of Texas Instruments exploitationsDLP system is optionally transmitted and come from The light of input source, and using controlled by the microchip for being referred to as Digital Micromirror Device (DMD) and be fixed on the DMD pixel- Representative micro mirror, by light projection into desired output pattern or mask (mask).DLP technologies are exploited for image projection system System, as the replacement display system based on LCD technology.With DLP system relevant outstanding image definition, brightness and uniformity Image resolution ratio and the vital addition process manufacture of accuracy can be perfectly suitable for, because the border of the light of projection The final border for defining the three-dimensional body that cure and produce.In addition, image projection system (such as LCD and DLP) provides Theoretic speed advantage, because they can make whole cross-sectional layer while exposure and curing.In addition, when based on laser When hardening time needed for system is proportional to the complexity of the cross section to be scanned, image projection system be considered with it is transversal Face is unrelated, it means that the time for exposure to given layer will not change with any increase to the shape complexity of given layer.This So that they are particularly suitable for the product with complicated and fine geometry that is manufactured by addition process.
DLP and LCD is not the alternative for itself producing light；And it there is provided a kind of by the light processing from existing light source Into the mode of more desirable pattern.Therefore, the same input light source for still needing coupling.Although it is input to image projection system Light can come from any source, including traditional lamp or even laser, but more generally useful, from one or more light emitting diodes (LED) input light is calibrated.
LED is the semiconductor devices that light is produced using electro optical phenomenon.Now, for addition process manufacture system Light of the LED light source launch wavelength between 300-475nm, wherein 365nm, 375nm, 395nm, 401nm, 405nm and 420nm are Common peak value spectrum output.On LED light source deeper into discussion refer to textbook " Light-Emitting Diodes ", E.Fred Schubert, the second edition,E.Fred Schubert 2006, are gone out by Cambridge University Press Version.LED is capable of providing following advantage：Compared to other light sources, they are longer to approach the efficiency continuous firing of peak value in theory Time.Moreover, compared with the light optic system based on laser, their usually more energy efficient and maintenance costs are low, so as to cause institute The initial cost and lasting cost having the right are relatively low.
Therefore, various addition process manufacture systems use one kind in following non-limiting optics profile instance：(1) only Laser, (2) laser/DLP, (3) only LED, (4) LED/DLP, or (5) LED/LCD.System without using DLP technologies also may be used To combine other calibration lens or condenser lens/mirror, so that light is optionally directed on liquid resin.
Recently, configured regardless of optics, newer addition process manufacture system has begun to more frequently use this The light source of sample, the light source launch radiation in the case where exporting more preferable wavelength than the tradition under 355nm.Other are from monochromatic light Transfer to select the light source of light of those transmittings with wider spectrum output distribution in source.Therefore, comprising based on laser/DLP, This newer system of the optics configuration of LED, LED/DLP or LED/LCD is had begun to more wider than common in the past Spatial distribution and longer wavelength peak value spectrum output operation.The wavelength wherein used is from 355nm to visible spectrum Direction movement, some even with to visible-range peak value spectrum export.Such longer wavelength is (i.e. from about 375nm To about 500nm) it is referred to as so far " ultraviolet/visible light ".
Some usually quoted of the current optics for being intended to be increasingly used in ultraviolet/visible light area are non- It is restricted the reason is that：(1) ultraviolet/visible light operated within range light source cost reduction (initial cost and maintenance cost two Person)；And (2) compared to deeper into UV areas transmitting and the light source of all other situation all same, ultraviolet/visible light light source with Lower energy transmitting radiation, therefore tissue is damaged smaller.This causes in accidental exposure, compared to those deeper into To the light source of UV areas work, the harmfulness smaller of ultraviolet/visible light light source.As the popularization of addition process manufacture is in consumer, " production The person of disappearing (prosumer) " and industry continue to increase in the segmenting market, and use relatively low, the less dangerous actinic radiation sources of utilization cost Addition process manufacture system become more and more important to cure the demand of liquid photopolymer.
However, it is not without noticeable cost using the benefit of ultraviolet/visible light light source/light optic system. So far, the shortcomings that maximum is the difficulty that exploitation is used to utilize the suitable photopolymer of the system of ultraviolet/visible light optics Spend relative increase.One of the main reasons is：In addition to the energy of longer wavelengths of light reduces this natural phenomena, business light source Intensity generally also with peak value spectrum output wavelength increase and reduce.Therefore, although traditional lamp based on 355nm laser System may provide 1500W/cm on resin surface2Irradiation level, but the known business system in work about at 400nm only About 1/1000 irradiation level of the irradiance value can be substantially provided in resin surface.In fact, for some more economical desktops For unit (desktop units), by the existing business addition process manufacture system based on 365nm or 405nm DLP The irradiation level of resin surface that provides of ultraviolet/visible light optics can be with as low as 0.1W/cm2Or even 0.0002W/cm2。 Emittance/intensity of these relative reductions causes by this ultraviolet/visible light optics in radiation curable resins Generation photopolymerization reaction is more difficult, unless open-assembly time becomes long.This considerably increases the structure time of product in turn, So as to reject the theoretical velocity advantage of photomask display system.In addition, in the market there are less light initiation system (particularly Cation light initiation system), to promote the photopolymerization under this longer ultraviolet/visible light wavelength.
Relative to system (for example, system based on 355nm laser) the available various options to work deeper into UV areas, Above-mentioned challenge causes the addition process manufacture system using the modern optical devices system to work in ultraviolet/visible light area available The limited amount of photopolymer.
For the system using ultraviolet/visible light device, it is known that there are the resin of free redical polymerization.This resin leads to Often by one or more (methyl) acrylate compounds (or organic compound of other free redical polymerizations) and for certainly The free radical photo-initiation generated by base forms.United States Patent (USP) No.5,418,112 describes a kind of such free-radical curable System.Although the relatively low energy that the resin of free redical polymerization is provided even in ultraviolet/visible light optics It is also easy to cure with relatively low intensity, but it is not suitable for all addition process manufacture applications.First, it is considered suitable for addition (methyl) acrylate based resin of method manufacturing process generally produces the mechanicalness for being incorporated in many final use applications The curing product of energy deficiency.Therefore, its product produced is usually not sufficiently strong for the application of non-prototype.Further, since The problem of overstrain caused by shrinkage during curing, this resin usually shows deformation, such as produce warpage Or lopsided product.This problem is aggravated in the addition process manufacture machine of large platform, wherein the shrinkage effect accumulated The product warpage or deformity cured when object becomes much larger should be exaggerated.These problem on deformation can be entangled by following software Just, which causes known shrinking percentage by changing the cad file from its generation stereoscopic three-dimensional product.However, software correction It is not enough to be fully compensated with complicated shape or needs across in the product of the close dimensional tolerance of long range Deformation.
Resin suitable for another well-known type of addition process manufacture system is " can to mix " cured resin, or Person includes those following：(1) compound of epoxides, oxetanes or other types of cationically polymerizable；(2) one Kind or a variety of cation light initiators；(3) compound of acrylate or other types of free redical polymerization；(4) One or more free radical photo-initiations.This example for mixing cured system is in such as United States Patent (USP) No.5,434,196 In be described.For a long time, it is known that the curing product that this resin can cause to produce by addition process manufacturing process has excellent In the mechanical performance of all acrylic ester base resin.It is also embodied in addition, cured system can be mixed better than all acrylic ester system： It is influenced smaller by the shrinkage problem of long-standing problem all acrylic ester system.
However, since the ring opening process of cationic polymerization is usually slower than radical polymerization and needs more activation energy Amount, so being substantially more difficult to ensure that this formulation for addition process manufacture application fully cures or successfully " build " three-dimensional article Body.Also, cure at least part after it can mix cured resin and be subjected to actinic radiation, the green compact being generated by it The mechanical strength (or " green strength ") of model is also not enough to be used in the manufacture application of many addition processes, the mechanical strength (or " green strength ") it is to be measured for example, by elasticity modulus or fracture strength.Compared with conventional system, with relatively low energy and by force The ultraviolet/visible light optics of degree transmitting radiation significantly exacerbates these problems.
Due to the limitation to cationic polymerization, so far, there is not yet the liquid for mixing known to addition process manufacture Body radiation curable resins, it is adapted to the more modern addition process manufacture system using ultraviolet/visible light optics.In addition, There is no liquid radiation curable resins manufactured for addition process-can mix curing or other-this addition processes that are used for manufacture Liquid radiation curable resins be suitable for using ultraviolet/visible light optics addition process manufacture system, while (1) Cure fast enough, (2) can assign enough mechanical strengths, and (3) anti-shrink or warpage properties, so as to prevent cured by its Three dimensional articles deform.
By mentioned earlier, it is clear that：Outstanding demand is to provide suitable for using ultraviolet/visible light light so far That learns the addition process manufacture system of device mixes cured fluid radiation resin combination, it can produce mechanical property at least Equal to the existing three dimensional articles for mixing curing materials designed by traditional 355nm system designs based on laser.
The content of the invention
This document describes the several embodiments of the present invention.The first embodiment is that the liquid manufactured for addition process can Ultraviolet/visible light radiation-curable composition, the composition include：Light-initiated bag, it further includes about 0.1 weight % to about The salt compounded of iodine cation light initiator of 15 weight %, the Norrish I types photoinitiator of about 0.1 weight % to about 5 weight %, about Accelerating agents and optional photosensitizer of the 0.1 weight % to about 15 weight %；The component of cationically curable, it is further included about The oxetanes of 1 weight % to about 20 weight %, the cycloaliphatic epoxides and about 2 weights of about 3 weight % to about 40 weight % Measure the glycidyl ether epoxides of % to about 40 weight %；The free redical polymerization component of about 5 weight % to about 40 weight %； With optional at most about one or more additives of 50 weight %.The Norrish I types of the composition of the first embodiment Photoinitiator be further have the alkyl of silicon, germanium, tin or lead atom-, the compound of aryl-or acyl group-substituted.
Second of embodiment be for addition process manufacture can ultraviolet/visible light radiation-curable composition, the combination Thing includes：First, light-initiated bag, it further includes salt cation photoinitiator, (itself is further includeed reducing agent The Norrish I type photoinitiators being dissolved in vinyl ether compound of effect amount, the vinyl ether compound is at 25 DEG C For liquid) and optional photosensitizer；Second, cationically polymerizable component；3rd, free redical polymerization component；4th, optional One or more additives.The Norrish I type photoinitiators of the composition of second of embodiment are additionally configured to passing through Enter triplet when being excited exposed to actinic radiation, if wherein combined according to the molecule modeling under B3LYP/6-31G (d) Koopman theorems (IP=- εHOMO) calculate, then the ionization potential (ionization potential) of the triplet of this excitation For from about 2.5eV or about 3.0eV to about 4.15eV, or to about 3.98eV, or to about 3.90eV, or to about 3.80eV, or to about 3.70eV or to about 3.55eV.
The third embodiment is to form three-dimensional system by using the addition process manufacture system of ultraviolet/visible light optics The method of product, the described method comprises the following steps：First, there is provided the first or second embodiment are appointed according to the present invention Where face be used for addition process manufacture liquid radiation-hardenable composition；Second, build the liquid radiation curable resins The first liquid level；3rd, make the first liquid level Imagewise exposure horizontal to form imaging in actinic radiation by optics Section, so as to form the first cured layer, the optics is configured as in about 375nm to about 500nm, or about 380nm is to about 450nm, or about 390nm is to about 425nm, or the peak value spectral intensity of about 395nm to about 410nm issue and penetrate radiation；4th, formed The mew layer of the liquid radiation curable resins contacted with first cured layer；5th, make the mew layer Imagewise exposure in photochemical Radiate to form other imaging cross section；6th, the 4th step and the enough number of the 5th step are repeated to build three-dimensional article.
4th kind of embodiment is to pass through using according to the composition of the first or second of embodiment according to the third The three-dimensional article that the method for embodiment is formed.
The other embodiment of the present invention is described below.
Brief description
Master drawing shown in Fig. 1 shows the conversion ratio % and the functional relation of time of two kinds of different components.
Describe in detail
In this document in the whole text, " ultraviolet/visible light " is defined as from greater than or equal to about 375 nanometers (nm) to being less than or wait In the electromagnetic spectrum area of about 500 nanometers (nm).
Therefore, in this document in the whole text, " ultraviolet/visible light optics " is defined as following any electric system, machinery system System or electro-mechanical system, system generation is and guided/is shown in be run under the peak value spectral intensity in ultraviolet/visible light region Actinic radiation.The specific non-limiting examples of ultraviolet/visible light optics include laser, LED, are coupled to DLP and show One or more LED of system, the one or more LED for being coupled to LCD display system, the laser for being coupled to DLP display systems Device and the laser for being coupled to LCD display system.
Composition according to the present invention at least contains light-initiated bag, cationically curable/cationically polymerizable component, can oneself Cure/free redical polymerization component and optional one or more additives by base, hereafter describe each of which successively.
Light-initiated bag
Composition according to the present invention contains light-initiated bag.Light-initiated bag is comprising tending to trigger, promote or catalytic chemistry The component for reacting or enabling chemical reaction to carry out, the chemical reaction cause or improve to be subjected to proper amount of actinic radiation (spy Be not the actinic radiation in visible range and/or ultraviolet spectra area) when given group compound in photopolymerization speed or amount.Light draws Most common part of giving out a contract for a project is one or more photoinitiators, but can in addition use photosensitizer, reducing agent as described herein And/or accelerating agent.Photoinitiator is (particularly photochemical in visible range and/or ultraviolet spectra area in absorption actinic radiation Radiation) when carry out light reaction, so as to produce the compound of reactive materials.These reactive materials can be catalyzed, trigger or into Row causes the chemical reaction of the physical property significant changes of suitable formulation.Therefore, photoinitiator be it is a kind of can be by the thing of light Reason can be converted to the compound of the appropriate chemical energy of reactive intermediate form.The photoinitiator of common type includes cationic photopolymerization Initiator and free radical photo-initiation.
Although photosensitizer can produce reactive materials when exposed to actinic radiation, they can with the main reason for be They have speed by improving light initiation polymerization or improve one or more by varying wavelength when polymerizeing The ability of the efficiency of related photoinitiator.Finally, reducing agent and accelerating agent be not straight when their own is exposed to photochemical reaction Practice midwifery raw reactive materials, but facilitate or accelerate rate of polymerization yet by indirect mechanism so that they are placed on therein group Overall conversion or inversion quantity (particularly epoxides and acrylate conversion) meeting in the case where they are not present of compound Reduce.In a preferred embodiment, when making bag by using the addition process manufacture system of ultraviolet/visible light optics When composition containing reducing agent and/or accelerating agent is subjected to actinic radiation, reducing agent and/or accelerating agent can improve rate of polymerization.
Cation light initiator
According to a kind of embodiment, liquid radiation-curable resin composition includes cation light initiator.Cationic photopolymerization Initiator triggers cation ring-opening polymerization when light irradiates.
In one embodiment, any suitable alkali cation light initiator, but iodo cation can be used Photoinitiator is preferable, such as with selected from diaryl group iodized salt, triaryl salt compounded of iodine, aromatic iodonium salts and its any combination Cation those.
In another embodiment, the cation of cation light initiator is selected from aryl diazonium salt, aromatics sulfonium salt, aromatics Salt compounded of iodine, Metallocenyl compound, Fang Zu phosphonium salts and its any combination.In another embodiment, cation is polymerization Sulfonium salt, such as in US5380923 or US5047568；Or other aromatics contain heteroatomic cation and naphthyl sulfonium salt, such as US7611817、US7230122、US2011/0039205、US2009/0182172、US7678528、EP2308865、 In WO2010046240 or EP2218715.In another embodiment, cation light initiator is selected from triarylsulfonium salt, two Aryl salt and compound and its any combination based on metallocene.Salt (such as salt compounded of iodine and sulfonium salt) and ferrocene salt Have the advantages that usually more thermally stable.
In a specific embodiment, cation light initiator there is anion selected from the group below：BF4 -、AsF6 -、 SbF6 -、PF6 -、[B(CF3)4]-、B(C6F5)4 -、B[C6H3-3,5(CF3)2]4 -、B(C6H4CF3)4 -、B(C6H3F2)4 -、B[C6F4-4 (CF3)]4 -、Ga(C6F5)4 -、[(C6F5)3B-C3H3N2-B(C6F5)3]-、[(C6F5)3B-NH2-B(C6F5)3]-, four (3,5- bis- is fluoro- 4- alkoxyl phenyls) it is borate, four (the fluoro- 4- alkoxyl phenyls of 2,3,5,6- tetra-) borates, perfluoroalkyl sulfate, three [(complete Fluoroalkyl) sulfonyl] methide, two [(perfluoroalkyl) sulfonyl] acid imides, perfluoroalkyl phosphate, three (perfluoroalkyls) Three fluorophosphates, double (perfluoroalkyl) four fluorophosphates, three (pentafluoroethyl group) three fluorophosphate and (CH6B11Br6)-、 (CH6B11Cl6)-And other halocarborane anion.
The summary of other salt initiators and/or metallocene salt is visible " UV Curing, Science and Technology ", (S.P.Pappas is compiled, Technology Marketing Corp., 642 Westover Road, Stamford, Conn., U.S.A.) or " Chemistry＆Technology of UV＆EB Formulation for Coatings, Inks＆Paints ", volume 3 (P.K.T.Oldring volumes).
In one embodiment, cation light initiator, which has, is selected from aromatics sulfonium salt, aromatic iodonium salts and Metallocenyl The cation of compound, and at least one are selected from SbF6 -、PF6 -、B(C6F5)4 -、[B(CF3)4]-, four (the fluoro- 4- methoxyl groups of 3,5- bis- Phenyl) borate, fluorinated alkyl sulfonate, perfluoroalkyl phosphate, three [(perfluoroalkyl) sulfonyl] methides and [(C2F5)3PF3]-Anion.
The example of cation light initiator suitable for other embodiment includes 4- [4- (3- chlorobenzene formacyls) phenyl Sulphur] double (4- fluorophenyls) the sulfonium hexafluoro antimonate of phenyl, double (4- fluorophenyls) sulfoniums of 4- [4- (3- chlorobenzene formacyls) phenyl sulphur] phenyl Double (4- fluorophenyls) sulfonium four (the bis- fluoro- 4- of 3,5- of four (pentafluorophenyl group) borates, 4- [4- (3- chlorobenzene formacyls) phenyl sulphur] phenyl Methoxyphenyl) borate, double (4- fluorophenyls) sulfonium four (2,3,5,6- tetra- of 4- [4- (3- chlorobenzene formacyls) phenyl sulphur] phenyl Fluoro- 4- methoxyphenyls) borate, three (4- (4- acetylphenyls) sulfur phenenyl) sulfonium four (pentafluorophenyl group) borates (come from BASF'sPAG 290), three (4- (4- acetylphenyls) sulfur phenenyl) sulfonium three [(trifluoromethyl) sulfonyl] methyl Compound is (from BASF'sGSID 26-1), three (4- (4- acetylphenyls) sulfur phenenyl) sulfonium hexafluorophosphates (come From BASF's270) and can be from the HS-1 that San-Apro Ltd are obtained.
In a preferred embodiment, cation light initiator component includes the following material individually or mixed：It is double The double hexafluoro antimonates of [4- diphenyl sulfoniums phenyl] thioether；Thio Phenoxyphenyl sulfonium hexafluoro antimonate (can be obtained from Chitec Chivacure 1176)；Three (4- (4- acetylphenyls) sulfur phenenyl) sulfonium four (pentafluorophenyl group) borates are (from BASF'sPAG 290)；Three (4- (4- acetylphenyls) sulfur phenenyl) sulfonium three [(trifluoromethyl) sulfonyl] methides (from BASF'sGSID 26-1)；Three (4- (4- acetylphenyls) sulfur phenenyl) sulfonium hexafluorophosphates (come from BASF's270)；[4- (1- Methylethyls) phenyl (4- aminomethyl phenyls) iodine four (pentafluorophenyl group) borate (energy Enough Bluesil PI 2074 obtained from Bluestar Silicones)；4- [4- (2- chlorobenzene formacyls) phenyl sulphur] phenyl is double (4- fluorophenyls) sulfonium hexafluoro antimonate (can be from the P-172 that Adeka is obtained)；SP-300 from Adeka；With with (PF6-m (CnF2n+1)m)-The aromatics sulfonium salt of anion, wherein m are 1 to 5 integer, and the integer that n is 1 to 4 (can be from San-Apro Ltd. Monovalence the sulfonium salt CPI-200K or CPI-200S of acquisition, can be from the TK-1 that San-Apro Ltd. are obtained or can be from San-Apro Ltd. the HS-1 obtained).
In one embodiment of the invention, the liquid radiation curable resins for addition process manufacture include aromatics three Aryl sulfonium salt cation light initiator.Purposes of the aromatics triarylsulfonium salt in addition process manufacture application is known.Refer to US 20120251841, the U.S.Pat.No.6 of Asahi Denki Kogyo of DSM IP Assets, B.V., 368,769, its Discuss aromatics triarylsulfonium salt and four aryl boric acid root anion, including four (pentafluorophenyl group) borates, and these chemical combination Purposes of the thing in stereolithography application.Triarylsulfonium salt is disclosed in such as J Photopolymer Science＆Tech (2000), 13 (1), 117-118 and J Poly Science, Part A (2008), 46 (11), in 3820-29.J Polymr Sci, Part A (1996), 34 (16), disclose triarylsulfonium salt Ar in 3231-32533S+MXn-With complexing metal halogen the moon from Son such as BF4 -、AsF6 -、PF6 –And SbF6 -。
The example of triaryl matte four (pentafluorophenyl group) borate cation light initiator has three (4- (4- acetylphenyls) sulphur Phenyl) sulfonium four (pentafluorophenyl group) borate.Three (4- (4- acetylphenyls) sulfur phenenyl) sulfonium four (pentafluorophenyl group) borate conducts PAG-290 from Ciba/BASF commercially it is known that can simultaneously obtain.
In another embodiment, cation light initiator is that have to use SbF6 -、PF6 -、BF4 -、(CF3CF2)3PF3 -、 (C6F5)4B-、((CF3)2C6H3)4B-、(C6F5)4Ga-、((CF3)2C6H3)4Ga-, trifluoromethayl sulfonic acid root, nine fluorine butane sulfonate radicals, The aromatics triarylsulfonium salt for the anion that Loprazolam root, butane sulfonate radical, benzene sulfonic acid root or p-methyl benzenesulfonic acid root represent.It is this Photoinitiator is for example described in United States Patent (USP) No.8,617,787.
Another cation light initiator is the aromatics triaryl matte sun for the fluorophosphoric acid root anion that there is fluoroalkyl to substitute Ionic photoinitiator.The business of the aromatics triaryl matte cation light initiator of fluorophosphoric acid root anion with fluoroalkyl substitution Example be can from CPI-200 that San-Apro Limited are obtained series (such asOr) or 300 series.
Also several commercially available cation light initiators, its be designed to especially suitable for absorb light and it is ultraviolet/can See generation photoreactivity material under optical wavelength.It is visible that one or more incorporations in these cation light initiators are used for UV/ It can be realized in the liquid radiation-hardenable composition of photocuring by " direct " excitation photoinitiator.Ultraviolet/visible light-straight Connecing some non-limiting examples of excitation cation light initiator includes：Irgacure 261,103 and of Irgacure PAG Irgacure PAG 121 (it is commercially available from BASF)；262 (η 5-2,4- cyclopentadiene -1- bases) [(1,2,3, 4,5,6- η)-(1- Methylethyls) benzene]-iron (I)-hexafluoro antimonate), it is commercially available from Chitec Technology Co.；With CPI-400 series of photoinitiators, it can be obtained from San-Apro Limited.
Unexpectedly, however, it is found by the applicant that：Above-mentioned ultraviolet/visible light directly excites cation light initiator usual It is unsuitable for realizing solid using fully mixing for the composition used in the addition process manufacturing process of ultraviolet/visible light optics Change.While not wishing to be bound by any theory, but can consider：Since the free base section of polymer network is with much higher speed Rate cures, so the radically curing part of resin constructs viscosity and polymer architecture, so as to significantly reduce slower curing Cationic curing material molecular mobility, and then significantly reduce integrally curing speed to unacceptable low rate.This A problem be it is double cure that hybrid resins are intrinsic, its longer wavelength of modern UV/visible light optical device, compared with low energy and Aggravate under relatively low strength characteristic.Therefore, applicant have discovered that：It is used for the conjunction of addition process manufacture under ultraviolet/visible light wavelength The suitable preparation for mixing cured radiation-hardenable composition be not by only change suitable for ultra-violet curing (for example, by based on The system of 355nm laser) hybrid resin in cation light initiator realize.Inventor has found：It is used for realization Suitably mix the modern addition that cured this " directly excitation " mechanism is insufficient for utilizing ultraviolet/visible light optics The processing status of method manufacture system.
On the contrary, applicant it was unexpectedly found that：In order to manufacture system using the addition process of ultraviolet/visible light optics Realize in system and sufficiently cure, need the combination of one or more replacement mechanisms on the contrary.It is by similar to photosensitization first " indirectly excitation " mechanism.Second is the cationic polymerization mechanism promoted by free radical.The third functionally similar mechanism It is the generation of active cation, the active cation is by ether that some photoinitiator fragments are added to vinyl ethers and are formed The oxidation of free radical and cause, also referred to as vinyl ethers flowcollector aggregation scheme FlowCollector.As discussed further below, it is formed according to the present invention For addition process manufacture radiation-hardenable composition further include other light-initiated bag key element such as reducing agent, accelerating agent and/ Or photosensitizer, synergistically to use the one or more in these mechanism, to include the addition of ultraviolet/visible light optics Realized in method manufacturing process and suitably mix curing.
Liquid radiation-curable resin composition can include any proper amount of cation light initiator, for example, some It is the at most about 15 weight % of resin combination in embodiment；In some embodiments, for resin combination at most about 5 weight %；In other embodiment, it is the about 2 weight % to about 10 weight % of resin combination；In other embodiment In, for the about 0.1 weight % to about 5 weight % of resin combination.In other embodiment, the amount of cation light initiator For the about 0.2 weight % to about 4 weight % of total resin composition；In other embodiments, it is about the 0.5 of total resin composition Weight % to about 3 weight %.
Free radical, especially Norrish I types photoinitiator
The composition of the present invention also includes free radical photo-initiation.According to a kind of embodiment, liquid radiation-hardenable tree Oil/fat composition includes light initiation system, and the light initiation system contains at least one photoinitiator for having the function of cation and triggering With at least one photoinitiator that there is free radical and trigger.Both contained in addition, light initiation system can be included on same molecule There is the photoinitiator that free radical triggers function to trigger function containing cation again.As described above, photoinitiator is due to the work of light With or synergistic effect between the effect of light and the electron excitation of sensitizing dyestuff and chemical change occurs, so as to produce freedom The compound of at least one of base, bronsted lowry acids and bases bronsted lowry.
In general, free radical photo-initiation is divided into：The photoinitiator of free radical is formed by cracking, it is referred to as " Norrish I types "；With the photoinitiator that free radical is formed by taking hydrogen by force, it is referred to as " Norrish II types ".Norrish II types are light-initiated Agent needs hydrogen donor, which plays the role of radical source.It is to be based on bimolecular reaction due to triggering, so Norrish II types photoinitiator is usually slower than the Norrish I type photoinitiators that the unimolecule based on free radical is formed.On the other hand, Norrish II type photoinitiators are typically considered to have more preferable absorbing properties in near-ultraviolet spectrum region.However, invention People has now been found that：II type photoinitiators are poorly suitable in composition according to the present invention, this is because due to they represent it is quick Agent and the oxidizable group such as such as combination of amine, it is expected that they can suppress cationic curing.
Aromatic ketone (such as benzophenone, thioxanthene ketone class, benzil and quinones) is in hydrogen donor (such as alcohol, amine or mercaptan) In the presence of photodissociation, result in the free radical (ketyl type free radical) that is produced from carbonyls and another supplied derived from hydrogen The free radical of body.The photopolymerization of vinyl monomer is typically to be triggered by the free radical of hydrogen donor generation.Due to steric hindrance and The delocalization of unpaired electron, ketyl radical is to vinyl monomer usually without reactivity.
In order to successfully be formulated for the liquid radiation curable resins of addition process manufacture, it is necessary to reexamine resin combination Present in photoinitiator wavelength sensitivity, so that it is determined that whether they will be selected for providing and cure the radiation source of light and live Change.
According to a kind of embodiment, the liquid radiation curable resins for addition process manufacture include at least one free radical Photoinitiator, the free radical photo-initiation are selected from benzoylphosphine oxide, aryl ketones, benzophenone, hydroxylated ketone, 1- Hydroxy phenyl ketone, ketal, metallocene and its any combination.
In one embodiment, the liquid radiation curable resins for addition process manufacture include it is at least one be selected from by Free radical photo-initiation in the group of following composition：2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, 2,4,6- trimethyls Benzoylbenzene base oxethyl phosphine oxide, double (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides, 2- methyl isophthalic acids-[4- (first Base sulphur) phenyl] -2- morpholinopropanone -1,2- benzyls -2- (dimethylamino) -1- [4- (4- morpholinyls) phenyl] -1- butanone, 2- dimethylaminos -2- (4- Methyl-benzvls) -1- (4- morpholines -4- bases-phenyl)-butyl- 1- ketone, 4- benzoyl -4'- methyl Diphenylsulfide, 4,4 '-bis- (diethylamino) benzophenone and 4,4'- pairs of (N, N'- dimethylamino) benzophenone (Michaelis Ketone), benzophenone, 4- methyl benzophenones, 2,4,6- tri-methyl benzophenones, dimethoxy-benzophenone, l- hydroxy cyclohexylphenyls Base phenyl ketone, phenyl (1- hydroxyisopropyls) ketone, 2- hydroxyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -2- methyl isophthalic acids-the third Ketone, 4- isopropyl phenyls (1- hydroxyisopropyls) ketone, oligomeric-[2- hydroxy-2-methyls -1- [4- (1- methyl ethylenes) benzene Base] acetone], camphorquinone, 4,4 '-bis- (lignocaine) benzophenone, benzil dimethyl ketal, double (η 5-2-4- rings penta 2 Alkene -1- bases) double [bis- fluoro- 3- of 2,6- (1H- pyrroles -1- bases) phenyl] titaniums and its any combination.
For launch 300-475nm wave-length coverages light source (be specially 365nm, 390nm or 395nm at transmitting that A bit), include in the example of the systemic appropriate photoinitiator in the region：Benzoylphosphine oxide, such as 2,4,6- trimethylbenzenes Formoxyl diphenyl phosphine oxide (the Lucirin TPO from BASF) and the oxidation of 2,4,6- trimethylbenzoyl phenyls ethyoxyl Phosphine (the Lucirin TPO-L from BASF), double (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides are (from Ciba's Irgacure 819 or BAPO), 2- methyl isophthalic acids--1 (Irgacure from Ciba of [4- (methyl sulphur) phenyl] -2- morpholines acetone 907), 2- benzyls -2- (dimethylamino) -1- [4- (4- morpholinyls) the phenyl] -1- butanone (Irgacure from Ciba 369), 2- dimethylaminos -2- (4- Methyl-benzvls) -1- (4- morpholines -4- bases-phenyl)-butyl- 1- ketone is (from Ciba's Irgacure 379), 4- benzoyl -4'- dimethyl diphenyl sulfides (the Chivacure BMS from Chitec), 4,4 '-it is bis- (diethylamino) benzophenone (the Chivacure EMK from Chitec) and double (N, N'- dimethylamino) the hexichol first of 4,4'- Ketone (michaelis ketone).Its mixture is also suitable.These acylphosphine oxide photoinitiators are preferably as they are irradiated in light When with good phosphono free radical delocalization.
A preferred embodiment of the invention, free radical photo-initiation are Norrish I type species.According to one kind Embodiment, free radical photo-initiation be alkyl-, the compound of aryl-or acyl group-substituted.In one embodiment, alkane Base-, aryl-or acyl group-substituted photoinitiator there is atom in carbon (the 14th race) race or with the original in carbon (the 14th race) race Centered on son.In this case, (radiated by excitation by absorbing), the 14th race's atom present in photoinitiator compound Form free radical.Therefore, this compound can produce with selected from carbon, silicon, germanium, tin and lead atom or using the atom as The free radical at center.In one embodiment, alkyl-, aryl-or acyl group-substituted photoinitiator be acyl group germanium compound.
In one embodiment, free radical photo-initiation is the germaniumbased compound with the structure of (I) according to the following formula：
Wherein Ar1It is aromatic group, its is unsubstituted or is further taken by one or more following groups in any position Generation：Alkyl diradical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, by one Or the aromatic group or heterocyclic group that multiple ethers, thioether, silylation, carboxyl or vinyl interrupt, or alkyl diradical, and Wherein R1、R2And R3Acyl group, aryl, alkyl or carbonyl can independently be, its it is unsubstituted or by one or more following groups into One step substitutes：Alkyl diradical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, The aromatic group or heterocyclic group interrupted by one or more ethers, thioether, silylation, carboxyl or vinyl, or alkyl are free Base.
In one embodiment, R1-R3In be each aryl substitution or aromatic acyl group.In a kind of embodiment In, R1-R3In have two be aryl substitution or aromatic acyl group, remaining substituent be C1-C10Or C1-C6Or C1-C3Alkyl.One In kind embodiment, R1-R3In have one be aryl substitution or aromatic acyl group, other two substituent be C1-C10Or C1-C6 Or C1-C3Alkyl.In another embodiment, R1-R3In be each C1-C10Or C1-C6Or C1-C3Alkyl.
In one embodiment, acyl group germanium photoinitiator is the compound for having one of following molecular structure：
In one embodiment, free radical photo-initiation is acyl group germanium compound.In one embodiment, acyl group germanium It is that benzoyltrimethyl germane (BTG) or double acyl group germanium acyl groups (bis acyl germanoyl) (can be from Ivoclar Commercially available from Vivadent AG, 9494Schaan/Liecthenstein)。
Another embodiment according to the present invention, free radical photo-initiation are acylphosphine oxide photoinitiators.It is such as beautiful State patent Nos.4,324,744,4,737,593,5,942,290,5,534,559,6,020,528,6,486,228 and 6,486, Acylphosphine oxide photoinitiator is disclosed in 226.
Acylphosphine oxide photoinitiator is double acylphosphine oxide (BAPO) or monoacylphosphine oxides (MAPO).
Double acylphosphine oxide photoinitiators have following formula：
Wherein R50To be unsubstituted or by 1 to 4 halogen or C1-C8Alkyl-substituted phenyl, cyclohexyl or C1-C12Alkane Base；R51And R52It is each independently other C1-C8Alkyl or C1-C8Alkoxy；R53For hydrogen or C1-C8Alkyl；And R54For hydrogen or Methyl.
For example, R50To be unsubstituted or by 1 to 4 C1-C4Phenyl, cyclohexyl or the C of alkyl, Cl or Br substitutions2-C10Alkane Base.Another embodiment is wherein R50For it is unsubstituted or in No. 2 positions, No. 3 positions, No. 4 positions or No. 2,5 positions by C1-C4Alkyl Substituted phenyl, cyclohexyl or C3-C8Alkyl.For example, R50For C4-C12Alkyl or cyclohexyl, R51And R52It is each independently another Outer C1-C8Alkyl or C1-C8Alkoxy；And R53For hydrogen or C1-C8Alkyl.For example, R51And R52For C1-C4Alkyl or C1-C4Alkane Epoxide；And R53For hydrogen or C1-C4Alkyl.Another embodiment is wherein R51And R52For methyl or methoxy and R53For hydrogen or Methyl.For example, R51、R52And R53For methyl.Another embodiment is wherein R51、R52And R53For methyl and R54For hydrogen.It is another Kind embodiment is wherein R50For C3-C8Alkyl.For example, R51And R52For methoxyl group；R53And R54For hydrogen and R50For iso-octyl.Example Such as, R50For isobutyl group.For example, R50For phenyl.Double acylphosphine oxide photoinitiators of the present invention are, for example, double (2,4,6- front threes Base benzoyl)-phenyl phosphine oxide (CAS#162881-26-7) or be double (2,4,6- trimethylbenzoyls)-(2,4- Double-amoxy phenyl) phosphine oxide.
Monoacylphosphine oxides photoinitiator has following formula：
Wherein R1And R2It is each independently unsubstituted or by halogen, C1-C8Alkyl and/or C1-C8Alkoxy substitutes 1-4 Secondary phenyl, benzyl, C1-C12Alkyl, or be cyclohexyl or-COR3Group, or R1For-OR4；R3For it is unsubstituted or by C1-C8Alkyl, C1-C8Alkoxy, C1-C8Alkyl sulfide and/or halogen substitute the phenyl of 1-4 times；And R4It is C1-C8Alkyl, phenyl or Benzyl.For example, R1It is-OR4.For example, R2It is unsubstituted or by halogen, C1-C8Alkyl and/or C1-C8Alkoxy substitutes 1-4 times Phenyl.For example, R3It is unsubstituted or by C1-C8Alkyl substitutes the phenyl of 1-4 times.For example, the monoacylphosphine oxides of the present invention It is 2,4,6- trimethylbenzoyl ethoxyl phenenyl phosphine oxides or 2,4,6- trimethyl benzoyl diphenyl base phosphine oxides.
Inventor it was unexpectedly found that：Some Norrish I types photoinitiators can particularly effectively promote it is ultraviolet/can See the cationic polymerization under photo curing condition.Inventor has found：This is probably to easily reduce (particularly iodine since they have ) salt ability, it is particularly true in the presence of this Norrish I types photoinitiator is with its relevant excited triplet state.It is actual On, inventor has found：The oxidation potential of this triplet for promote gratifying cationic polymerization level be it is important, when The composition being associated with is particularly true when being used in the addition process manufacturing process using ultraviolet/visible light optics. Regrettably, the oxidation potential that these excited triplet states are directly measured by cyclic voltammetry is nearly impossible, because its Service life is extremely short.However, inventor has devised a kind of alternative, (that is, one is lost by the ionization potential of compositions derived therefrom Energy (X=energy → X needed for its electronics++e-) quantify the oxidation potential of the component.By using B3LYP/6-31G (d) sides The Quantum mechanical calculation of method obtains ionization potential with the combination of Koopman theorems, and Koopman theorems point out that ionization potential can quilt The negative value of the orbital energy of highest occupied molecular orbital (HOMO) is calculated as, or is expressed as equation：IP=- εHOMO。
Therefore, in a preferred embodiment, Norrish I type photoinitiators as selection, its triplet electricity It is less than 4.15 electron-volts (eV) from potential, more preferably less than 3.98eV, more preferably less than 3.90eV, more preferably less than 3.80eV, more preferably less than 3.70eV, more preferably less than 3.55eV.In addition, in a preferred embodiment, selection is so Norrish I type photoinitiators, its triplet ionization potential is at least 2.5eV, more preferably at least 3.0eV.
Inventor is also unexpectedly found that：In order to further promote cationic polymerization horizontal (more by promoting to produce Cation), it is useful to select Norrish I type photoinitiators, and the Norrish I types photoinitiator is not only interim triple Reduce relevant cation light initiator under state, but also can be formed and be otherwise engaged in cation light initiator (preferably iodine Salt) redox reaction free radical.This free radical can be formed according to any mechanism, including (but being not necessarily limited to) is split Solve, take hydrogen, addition and tail by force and sting (backbiting).Therefore, the molecule modeling under B3LYP/6-31G (d) and Koopman theorem phases It is known with the one or more relevant various free radicals of Norrish I type photoinitiators as described herein with reference to applying also for calculating Ionization potential.Although these values are herein with the ionization potential (electricity of the excited triplet state with Norrish I type photoinitiators Sub- volt or eV) identical unit represents, but should not be directly compared with it.On the contrary, these values can only be used to examine relative to each other Consider.
Therefore, in a preferred embodiment, Norrish I type photoinitiators as selection, its it is known by with It is set to form such free radical, which, which has, is less than or equal to 5.50eV, more preferably less than 5.00eV, more preferably less than 4.80eV, and the calculating ionization potential of at least about 4.05eV.
Inventor is unexpectedly further discovered that：Formed by some Norrish I type photoinitiators described above Free radical be easy to add to component (the particularly vinyl with the electron donating group being connected with vinyl described below Ether) for further promote in the addition process manufacture application using ultraviolet/visible light optics the composition middle-jiao yang, function of the spleen and stomach that uses from The amount and/or speed of son polymerization are especially desired to.This is because obtained addition compound product is recognized as can be used for participating in oxygen Change/reduction reaction, therefore it reduces cation light initiator (the particularly cation light initiator of salt compounded of iodine type), so as to be formed Other active cation.Given data amount in document on this concept is very limited, but summarizes some values as follows：
1:J.Lalevee,X.Allonas,J.P.Fouassier,Chem.Phys.Lett.469,298(2009).
2:H.Fisher,L.Radom,Angew.Chem.Int.Ed.40,1340(2001)。
Therefore, in a preferred embodiment, composition contains Norrish I type photoinitiators, the Norrish I type photoinitiators are configured as producing such free radical, and the free radical addition is to the supplied for electronic being connected with vinyl The speed of the component (preferred vinyl ether) of substituent is more than 104M-1s-1, more preferably 105M-1s-1, most preferably equal to or greater than 3 ×105M-1s-1。
Liquid radiation curable resins for addition process manufacture can include any a effective amount of free radical photo-initiation, For example, in some embodiments, relative to the weight of all compositions, in an amount of from most about 10 weight %；In some implementations It is the about 0.1 weight % to about 10 weight % of resin combination in mode；In other embodiment, it is resin combination About 0.5 weight % to about 6 weight %；In other embodiment, it is about 1 weight % to about 3 weight %.
Photosensitizer
In some embodiments, the wavelength depending on the light for curing liquid radiation curable resins, desirable for liquid Radiation-curable resin composition includes photosensitizer.It is (particularly logical that term " photosensitizer " is often referred to increase light initiation polymerization speed Cross the wavelength changed when the related effective induced polymerization of photoinitiator occurs) any material；Referring to the textbook of G.Odian, Principles of Polymerization, the 3rd edition, 1991, page 222.Photosensitizer is usually by absorbing electromagnetic spectrum Ultraviolet or visible region in light, be then transferred to adjacent molecule and work.Many photosensitizers as described herein Make the associated cation photoinitiator " photosensitizer " in composition.Under ultraviolet/visible light wavelength, at least, salt compounded of iodine sun is utilized During ionic photoinitiator, this photosensitizer is usually easier generation.Working with together with photoinitiator (otherwise just cannot absorb foot The light of enough specific wavelengths) material be considered working by " excitation indirectly " mechanism and photoinitiator associated there. Applicant is suitable for passing through the cured composition of the invention of ultraviolet/visible light optics using this mechanism to prepare.
Multiple compounds can be used as photosensitizer, including heterocycle and condensed ring aromatic hydrocarbon, organic dyestuff and aromatic ketone.Light Quick dose of example includes being selected from those listed below photosensitizer：Ketone class, xanthene ketone (xanthenones), pyrene methanol class, anthracene Class, pyrene, quinones, xanthene ketone (xanthones), thioxanthene ketone class, benzoyl ester (benzoyl ester), benzophenone Class, and its any combination.The specific example of photosensitizer includes being selected from those listed below photosensitizer：[4- [(4- aminomethyl phenyls) sulphur] Phenyl] phenvl-methanone, isopropyl -9H- thioxanthene-9-ones, 1- pyrenes methanol, 9- (methylol) anthracene, 9,10- diethoxies anthracene, 9, 10- dimethoxys anthracene, 9,10- dipropoxies anthracene, 9,10- dibutoxies anthracene, 9- anthryl carbinols acetic acid esters, 2- ethyl -9,10- diformazans Epoxide anthracene, 2- methyl -9,10- dimethoxys anthracene, the 2- tert-butyl group -9,10- dimethoxys anthracene, 2- ethyl -9,10- diethoxy anthracenes With 2- methyl -9,10- diethoxies anthracene, anthracene, anthraquinone, 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl groups anthraquinone, 1- chloroanthraquinones, 2- amyl anthraquinones, thioxanthones and xanthone, isopropyl thioxanthone, 2-chlorothioxanthone, 2,4- diethyl thioxanthones, the chloro- 4- third of 1- Epoxide thioxanthones, methyl benzoylformate (the Darocur MBF from BASF), 2- benzoyl methyl benzoates (come from The Chivacure OMB of Chitec), 4- benzoyl -4'- methyldiphenyls thioether (the Chivacure BMS from Chitec), 4,4 '-bis- (lignocaine) benzophenone (the Chivacure EMK from Chitec), and its any combination.
The various light that novel mixture can also contain the transmitting beta radiation to different wave length and have different sensitivity draw Agent is sent out, to better profit from UV light sources.There is the use of the known photoinitiator of different sensitivity to transmitting beta radiation in addition Method manufacturing field is known, and can be selected according to the radiation source of such as 351nm, 355nm, 365nm, 385nm and 405nm Select.In this context, it is advantageous that so select various photoinitiators, and be used so that with a certain concentration by institute Emission lines produce identical optical absorption.
In one embodiment, photosensitizer is fluorone, such as bis- iodo -3- butoxy -6- fluorones of 5,7-, 5,7- Two iodo -3- hydroxyl -6- fluorones, bis- iodo -3- hydroxyl -6- fluorones of 9- cyano group -5,7-, or photosensitizer is
And its any combination.
When using photosensitizer, the other photoinitiators absorbed under shorter wavelength can be used.This photoinitiator Example includes：Benzophenone, such as benzophenone, 4- methyl benzophenones, 2,4,6- tri-methyl benzophenones and dimethoxy Base benzophenone, and 1- hydroxy phenyl ketone classes, such as l- hydroxycyclohexyl phenyl ketones, phenyl (1- hydroxyisopropyls) first Ketone, 2- hydroxyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -2- methyl isophthalic acids-acetone and 4- isopropyl phenyls (1- hydroxyisopropyls) Ketone, benzil dimethyl ketal and oligomeric-[2- hydroxy-2-methyls -1- [4- (1- methyl ethylenes) phenyl] acetone] (come from The Esacure KIP 150 of Lamberti).
It may be noted that：Some cation light initiators have low absorption at preferable photochemistry wavelength.For example, one In kind embodiment, addition process interested manufacture application is using in the UV/ optics about at 400nm with peak strength. Salt compounded of iodine (such as the Bluesil PI 2074 of Bluestar Silicones are available from, it is available from the Irgacure 250 of Ciba Iodine (4- aminomethyl phenyls) [4- (2- methyl-propyls) phenyl]-hexafluorophosphate (1-), and it is available from GE Silicones' UV9380c) there is directly absorbing for deficiency at preferable wavelength, it is therefore desirable to excessively concentration, sensitizer or some other machines System is sufficient light-initiated to induce.Therefore, absorbed sometimes using triplet sensitizer (such as thioxanthene ketone class and Michelers ketone) Actinic energy, then transfers energy into iodine initiator in an efficient way.However, thioxanthones and Michelers ketone tendency In formed orange or red, there are safety issue, although and they have obvious photochemistry be absorbed into 430nm, Under the curing optical wavelength of about 400nm, they cannot effectively be sensitized light reaction.
Therefore, in one embodiment, chloropropyl thioxanthones (CPTX) is the suitable sensitizer of iodine initiator, especially It is to be used in stereolithography, because it without significant light absorbs and produces the shallower system of color in more than 500nm Product.
In order to reduce the concentration of the sensitizer used in preparation and prevent may by rather high concentration sensitizer to combination Adverse effect caused by the final physical property of thing, being preferably used in 400nm has the sensitizer of high extinction coefficient.For example, two Benzophenone may act as triplet sensitizer in some cases, but for example in the frequency tripling YAG laser of work about at 355nm Under the optical maser wavelength of device (Coherent AVIA model #355-1800), extinction coefficient is about 108 liters/mole-cm.It is another Aspect, using identical laser, when under the same laser wavelength of about 400nm, extinction coefficient the disappearing for benzophenone of CPTX Almost 25 times of backscatter extinction logarithmic ratio (2585 liters/mole-cm).This shows：The CPTX of about 1/25 concentration may be only needed to come in preparation Equivalent optical absorption is provided.Therefore, in the case where curing optical wavelength and being more than 380nm, sensitizer preferably (but is not required ) have higher than 300 liters/mole-cm or higher (such as higher than 1000 liters/mole-cm, preferably above 2000 liters/rub You-centimetre) extinction coefficient.
Although the activity of cation light initiator can be improved using CPTX by teaching, trigger with above-mentioned cationic photopolymerization The sensitizer that agent is applied in combination is not necessarily limited to this.Multiple compounds can be used as photosensitizer, including heterocycle and condensed ring aromatic Hydrocarbon, organic dyestuff and aromatic ketone.The example of sensitizer includes JV Crivello in Advances in Polymer Science, Compound and K.Dietliker disclosed in 62,1 (1984) in J.V.Crivello＆K.Dietliker, “Photoinitiators for Cationic Polymerization”,Chemistry&technology of UV&EB Formulation for coatings, inks＆paints. Section III are rolled up, Photoinitiators for free radical and cationic polymerization；[P.K.T.Oldring volumes], SITA Technology Ltd, London, 1991 Disclosed in compound.Instantiation include more aromatics hydrocarbons and their derivates (such as anthracene, pyrene and its derivative), substitution Thioxanthones, alpha-hydroxyalkyl benzophenone, 4- benzoyl -4'- dimethyl diphenyl sulfides, acridine orange and benzoflavine (benzoflavin)。
In one embodiment, the description of the photosensitizer that photosensitizer usually can be according to a second aspect of the present invention is selected Select.In a preferred embodiment, photosensitizer used has structure according to the following formula：
Wherein R contains C1-C20Aliphatic chain.
In the preferred embodiment of a third aspect present invention, photosensitizer used is the photoinitiator based on anthracene. Commercially available this photosensitizer includes can be from the Anthracure that Kawasaki Chemical are obtainedTMUVS-1101 and UVS-1331.
In embodiments of the present invention, photosensitizer is optional components.In embodiments, particularly in light-initiated bag The combination of other components makes it possible under providing the condition of cure that they are subjected to fully in the case of polymerization, it is not necessary to individually Photosensitizer.However, in some such situations, extra photosensitizer still can be included, is not configured to further significantly Increase the speed or amount of photoinduction polymerization, but the penetration depth (Dp) of its resin of incorporation is controlled as UV absorbents.This Allow makers-up to be directed to and adjust resin with the addition process manufacturing process for it is expected cured thickness, without negatively affecting the thickness When solidification rate.This will be merged in as understood by those skilled.
If you are using, the liquid radiation curable resins for addition process manufacture can include any proper amount of light Quick dose, such as in some embodiments, in an amount of from the 0.1 weight % to 10 weight % of resin combination；In some embodiment party It is the about 1 weight % to about 8 weight % of resin combination in formula；In other embodiment, it is about the 2 of resin combination Weight % to about 6 weight %.In one embodiment, above range is particularly suitable for being used together with epoxy monomer.Another In kind of embodiment, the dosage of photosensitizer can be the about 0.05 weight % mixed with the weight of the total composition of the photosensitizer to about 3 weight %, or 0.5 weight % to 2 weight %.
Reducing agent
As used herein, reducing agent is in the fluid radiation composition for addition process manufacture according to the present invention Lost during polymerization in oxidation/reduction chemical reaction or " offers " one or more electronics enable to produce activity it is positive from The component of son.Although this component is in being subject to the effect of outside stimulus thing (such as in the actinic radiation for being subject to ultraviolet/visible light wavelength When dissociate) after form free radical before may not have the ability that electronics is easily provided, but they are regarded as being adapted to this hair The reducing agent of improving eyesight.Under any circumstance, in this redox reaction, it is stated that reducing agent reduces cationic photopolymerization initiation Agent (or derivatives thereof), thus their own (or after being subject to outside stimulus thing to act on, its free radical) is aoxidized.
The photoinitiated cationic polymerization of monomer (such as epoxides and vinyl ethers) mix cure addition process manufacture should Necessary effect is played in.Due to the additive used in different application, when using specific spectral sensitivity as target, light The length flexible of initiation becomes the Fundamentals for the curing performance for determining particular formulations.Therefore, it is (such as modern to longer wavelength Ultraviolet/visible light optics launched those) light initiation system of especially sensitive cationic polymerization is more and more important.Perhaps The existing light initiation system for being chiefly used in cationic polymerization is based on using some salt, such as diphenyl iodnium, triphenyl sulfonium salt With alkoxy pyridines salt.However, unless extra chromophore is merged in salt structure, otherwise these salt are in ultraviolet/visible light Do not absorbed significantly in spectral regions (in the event of if).It is therefore important that substitution method is found, by the salt easily obtained Range of sensitivity synthesis expands to ultraviolet/visible light wavelength, is especially considering that and has been designed in ultraviolet/visible light spectrum The commercially available photoinitiator absorbed is not suitable for being incorporated to due to other reasons mixes this in curing system for addition process manufacture Actual conditions.
As discussed herein, inventor by means of the combination of sensitizer by the mechanism that is referred to as exciting indirectly extremely Small part has reached expected purpose.In addition, salt is respectively in the redox reaction with free radical, charge transfer complex Electron donor compound and sensitizer long term electron excitation state in serve as electron acceptor.In these methods, so-called " from By base promote " cationic polymerization seemingly produce can trigger monomer cationic polymerization cationic substance one kind additionally have Effect and flexible mode.Integrated mechanism be related to by salt (On+) with suitable reduction potential aoxidize that photochemistry formed from By base：
R·+On+→R++On· (1)。
Non-limiting list for the Suitable reducing agent for the cationic polymerization for promoting free radical promotion generally includes amine, benzene Acyloin and its derivative, acylphosphine oxide, alkyl-, the germanium compound of aryl-or acyl group-substituted, phthalic aldehyde, vinyl halide Compound and polysilane.Many free radical photo-initiations as described herein, particularly relevant Norrish I type free radicals are light-initiated Agent, can additionally or alternatively use as suitable reducing agent.
Amine is considered as effective hydrogen donor, and easily forms free radical by chain tra nsfer mechanism, free radical can reduce with Its relevant cation light initiator.Therefore, in some embodiments, they can serve as suitable reducing agent.However, will These compounds be included in be used for addition process manufacture can be in the cured composition of chaotic radiation when need it is careful, because it is known that it Contained nitrogen-atoms tend to suppress cationic polymerization in other ways.
There are several systems that oxidable free radical is produced in the presence of ultraviolet/visible light light source.For example, contained by irradiation The free radical that the system for having xanthene dye and aromatic amine is formed can serve as the reducing agent of diphenyl iodnium.Similarly, when When salt is used together, decacarbonyldimanganese-organohalogen compounds combination is that cationic polymerization has under ultraviolet/visible light wavelength Imitate reducing agent.In addition, business titanocenes photoinitiator (such as Irgacure 784) may be used as by using visible light exposure The reducing agent source of generation.
Acylphosphine oxide and acyl phosphate with different structure have been used as the photoinitiator of radical polymerization.To acyl Photochemical widely studied display of base phosphine oxide：They undergo the α cracking of quite high quantum yield.
In one embodiment, acylphosphine oxide is to promote appropriate monomer cation under ultraviolet/visible light wavelength to gather The Suitable reducing agent of conjunction.Under ultraviolet/visible light wavelength, in the presence of double acylphosphine oxides and diphenyl iodnium, irradiation When can easily trigger the cationic polymerization of tetrahydrofuran and butyl vinyl ether.Without wishing to be bound by theory, it is believed that： Light-initiated double acylphosphine oxides easily capture hydrogen from appropriate donor (such as solvent or monomer) so that its with sun from Become reducing agent when sub-light initiator is used together.Caused carbon free radical placed in the middle with PhI+ ionic reactions by being converted Into carbocation, carbocation triggers cationic polymerization.As disclosed herein, it has been found that acylphosphine oxide (more preferably takes The acylphosphine oxide in generation) with the combination of suitable salt (such as salt compounded of iodine and pyridiniujm) promoted in UV/ visible-light curings Effective and efficient reducing agent of free cationic polymerization under wavelength.The Solicitation mechanism proposed seems to be related to light in the first step Generate phosphono (phosphinoyl) free radical and benzoyl free radical.Then phosphono free radical is aoxidized by salt to produce Life can trigger monomer polymerization phosphonium ions.The efficiency of latter step should be by the redox potential and phosphono free radical of salt Electron delocalization (p- features) control.Therefore, one embodiment of the present invention be maximum salt dissolving and acylphosphine oxide from By the oxidation-reduction potential between base photoinitiator, while also seek to the acyl group oxidation with maximum electron delocalization (p- features) Phosphine, so that the influence of this mechanism maximizes under 400nm wavelength lights and realizes maximum cationic curing speed.
Reducing agent can include two or more compounds.Applicant it was unexpectedly found that：When being dissolved at 25 DEG C During in the vinyl ether compound of liquid, a effective amount of Norrish I types photoinitiator (including alkyl-, aryl-or acyl group- Substituted germanium compound) serve as specially suitable reducing agent to promote the generation of active cation, when with (including iodine) salt Cation light initiator is particularly true when matching.
Liquid radiation curable resins for addition process manufacture can include any proper amount of for reducing cation The reducing agent of photoinitiator, such as be 0.01 to 30 weight % of resin combination in some embodiments；Other preferred In embodiment, it is the 0.01 weight % to 10 weight % of resin combination, is resin combination in other certain embodiments About 1 weight % of thing to about 8 weight %；In other embodiment, it is the about 2 weight % to about 6 weights of resin combination Measure %.In one embodiment, above range is particularly suitable for the use of salt compounded of iodine photoinitiator.In one embodiment, together A kind of reducing agent component can function simultaneously as free radical photo-initiation and reducing agent, thus promote at the same time radical polymerization and sun from Son polymerization.In another embodiment, the dosage of reducing agent can be the pact mixed with the weight of the total composition of the reducing agent 0.05 weight % to about 4%.
Accelerating agent and/or compound with the electron donating group being connected with vinyl
The extra component with the electron donating group being connected with vinyl that includes can be used for according to the present invention group In compound.In addition this component (it is referred to alternatively as accelerating agent) can provide a kind of mechanism, be used to make to improve by the mechanism With the cationic curing of the liquid radiation-hardenable composition of the addition process manufacture system of ultraviolet/visible light optics.Specifically For, inventor is also unexpectedly found that：When the other component (examples for inducing other reaction mechanisms as described herein with existing Such as suitable Norrish I types photoinitiator, photosensitizer and/or reducing agent) when, comprising with the supplied for electronic being connected with vinyl The additional component of substituent can cooperate with the speed and/or amount for improving and polymerizeing.
One preferred embodiment of the component with the electron donating group being connected with vinyl is vinyl ethers.Vinyl ethers It can be made of a variety of starting materials, such as ether, ester or double carbamate, or (poly-) urethane or carbonic acid of vinyl ethers end-blocking Ester.Some respective non-limiting examples are as described below：
Vinyl ethers can include the vinyl ether monomers from ether.The instantiation bag of vinyl ether monomers from ether Polyfunctional vinyl ether is included, it further comprises divinyl ether, such as ethylene glycol divinyl ether, diethylene glycol divinyl base Ether, triethyleneglycol divinylether, polyethylene glycol divinyl ether, propane diols divinyl ether, dipropylene glycol divinyl ether, Isobutyl vinyl ether, butanediol divinyl ether, butanediol divinyl ether, hexane diol divinyl ether, hexamethylene Divinyl ether, bisphenol-A epoxy alkane divinyl ether (bisphenol A alkylene oxide divinyl ) and Bisphenol F epoxy alkane divinyl ether ether；And polyfunctional vinyl ether, such as trimethylolethane trivinyl base ether, Trimethylolpropane tris vinyl ethers, trimethylolpropane tetravinyl ether, glycerine trivinyl ether, pentaerythrite tetravinyl Ether, pentaerythrite divinyl ether, five vinyl ethers of dipentaerythritol, six vinyl ethers of dipentaerythritol, trimethylolpropane The ethylene oxide adduct of trivinyl ether, the propylene oxide adduct of trimethylolpropane tris vinyl ethers, double trihydroxy methyls The ethylene oxide adduct of propane tetravinyl ether, the propylene oxide adduct of double trimethylolpropane tetravinyl ether, season penta The ethylene oxide adduct of tetrol tetravinyl ether, the propylene oxide adduct of pentaerythrite tetravinyl ether, dipentaerythritol The ethylene oxide adduct of six vinyl ethers, the propylene oxide adduct of six vinyl ethers of dipentaerythritol.
Vinyl ether monomers may be derived from double carbamate.Example includes polyfunctional vinyl ether, such as diethyl Alkenyl adipate ester, divinyl terephthalate, divinyl cyclohexyl dicarboxylic acid ester.Double [4- (vinyl oxygen) butyl] Adipate ester (4060), double [4- (vinyl oxygen) butyl] succinates (4030) it is, double [4- (vinyl oxygen) butyl] isophthalic acid ester (4010), double [4- (ethene yloxymethyl) cyclohexyl first Base] glutarate (4020), three [4- (vinyl oxygen) butyl] trimellitates ( 5015), double [4- (ethene yloxymethyl) cyclohexyl methyl] isophthalic acid esters (4040), double [4- (ethene Base oxygen) butyl] (4- methyl isophthalic acids, 3- phenylenes) diurethane (And double [4- (vinyl oxygen) 4220) Butyl] (two -4,1- phenylenes of methylene) diurethane (4210) etc..
The urethane or carbonic ester that vinyl ether monomers can be blocked with vinyl ethers.Instantiation includes polyfunctional vinyl Ether, such as with hydroxyvinyl ether capped polyurethane or makrolon, wherein including at least hydroxyl and second in same molecule Both alkenyl ether groups.Example includes but not limited to 2- hydroxyethyl vinylethers, 3- hydroxypropyls vinyl ethers, 2- hydroxypropyl ethene Base ether, 2- hydroxyisopropyls vinyl ethers, 4- hydroxy butyl vinyl ethers, 3- hydroxy butyl vinyl ethers, 2- hydroxy butyl vinyl ethers, 3- hydroxyisobutyls vinyl ethers, 2- hydroxyisobutyls vinyl ethers, 1- methyl -3- hydroxypropyls vinyl ethers, 1- methyl -2- Hydroxypropyl vinyl ethers, 1- hydroxymethyls propyl vinyl ether, 4- hydroxy-cyclohexyls vinyl ethers, 1,6- hexane diol list second Alkene ether, 1,4 cyclohexane dimethanol mono vinyl ether, 1,3- cyclohexane dimethanol monovinyl ethers, 1,2- cyclohexanedimethanols Mono vinyl ether, paraxylene monovinyl ether, meta-xylene monovinyl ether, ortho-xylene monovinyl base Ether, diethylene glycol monovinyl base ether, triethylene glycol mono vinyl ether, tetraethylene glycol mono vinyl ether, five ethylene glycol mono-vinyl Ether, oligoethylene glycol mono vinyl ether, polyethylene glycol mono vinyl ether, dipropylene glycol mono vinyl ether, tripropylene glycol list ethene Base ether, four propane diols mono vinyl ethers, these derivative, such as five propane diols mono vinyl ethers, oligomeric propane diols list ethene Base ether and polypropylene glycol mono vinyl ether, etc..
In a preferred embodiment, accelerating agent or component with the electron donating group being connected with vinyl are One or more among below：Vinyl ethers, vinyl esters, vinyl sulfide, positive vinyl carbazole, positive ethenyl pyrrolidone Ketone, positive caprolactam, allyl ether and vinylcarbonates.
In another preferred embodiment, there is the accelerating agent or component of the electron donating group being connected with vinyl It is polyfunctional.
Component (such as vinyl ethers) with the electron donating group being connected with vinyl is considered as adding for a long time The component used into the liquid radiation-hardenable composition of method manufacture.Traditionally, they are used as the network struction of " passive " Polymerizable components.This component has not used in the manufacture application of many addition processes, because it is known that they can be copolymerized Close；Heteropolymer caused by it is expected that can cause poor physical property in related three dimensional articles, when more excellent with other The monomer (such as cycloaliphatic epoxides, oxetanes and/or tetraglycidel ether epoxy resin) of choosing is particularly true when comparing. In addition, although this component can be cationically polymerizable, the known product that they tend to cause them to be solidified into Shrinkage and/or deformation increase, when with the ring-opened monomer of other cationic polymerizables (such as epoxides, oxetanes Or butyl oxide link (oxolane)) compared to when it is particularly true.Finally, although it is known they usually than many other monomer components (such as Ring-opened monomer such as epoxides or oxetanes) faster cure, but including for they does not go through usually, because overall (sun Ion) cure only be equivalent to its most slow separate constituent.
It is included in without considering vinyl ethers as cationically curable and/or free-radical curable monomer and is used for addition legal system In the radiation-hardenable composition made, vinyl ethers be not yet added in composition with accelerate or promote it is any it is adjoint can sun Extra (or faster) of cationic cure monomer such as epoxides cures.Inventor it was unexpectedly found that-especially in some purples Under the conditions of outside/visible-light curing-this compound in incorporation according to the present invention light-initiated bag when, peomote adjoint The rate of polymerization of cationically curable component such as epoxides or oxetanes and/or significantly improving for amount.This makes it possible to The three-dimensional micromodule that quick production is produced by using the addition process manufacturing process during ultraviolet/visible light optics, and it is produced Product there is excellent green strength and solid mechanical performance, be otherwise impossible according to known preparation method.
Inventor is also unexpectedly found that：In order to further promote cationic polymerization horizontal (more by promoting to produce Cation), selection with the accelerating agent of electron donating group or component being connected with vinyl be it is useful, the accelerating agent or Component can be formed easily work free radical based on vinyl to reduce cation light initiator (preferably salt compounded of iodine) or Ether free radical.Molecule modeling under B3LYP/6-31G (d) is combined with Koopman theorems to be applied also for calculating known and one kind Or a variety of electron donating groups being connected with vinyl are (such as, but not limited to trifluoromethyl vinyl ethers, vinyl acetate, three (trimethylsilyl) silylation vinyl ethers, vinyl sulfide and vinyl ethers) relevant various free radicals ionization potential. What although these values were formed with the ionization potential of the excited triplet state with Norrish I type photoinitiators and by it herein The identical unit of the ionization potential (electron-volt or eV) of free radical represents, but should not be directly compared with it.On the contrary, these values are only Available for considering relative to each other.
Therefore, in a preferred embodiment, promotion of the selection with the electron donating group being connected with vinyl Agent or compound, be configured to form known to the accelerating agent or compound with less than or equal to 6.58eV, more preferably less than The freedom of the calculating ionization potential of 5.42eV, more preferably less than 4.89eV, more preferably less than 4.30eV, more preferably less than 4.20eV Base, the ionization potential are that the molecule modeling under logical B3LYP/6-31G (d) calculates.In addition, in a kind of preferred embodiment In, selection is with the accelerating agent or compound of electron donating group being connected with vinyl, known to the accelerating agent or compound It is configured to form the free radical of the calculating ionization potential with least 3.3eV, more preferably at least 3.5eV, more preferably 3.8eV.
Without considering their Slurry pump, above-mentioned accelerating agent or component with the electron donating group being connected with vinyl In it is one or more can be used for any suitable amount in the composition of the present invention, and can be used alone or it is a kind of or A variety of type combinations enumerated herein use.In a preferred embodiment, relative to the gross weight of composition, have with The accelerating agent for the electron donating group that vinyl is connected or the amount of component are about 1 weight % to about 25 weight %, more preferably About 5 weight % to about 20 weight %, more preferably from about 5 weight % are to about 12 weight %.In another embodiment, have and second The accelerating agent for the electron donating group that alkenyl is connected or the amount of component are 1 weight % to 15 weight %, more preferably 1 weight % To 10 weight %, more preferably 3 weight % to about 8 weight %.In another embodiment, there is the power supply being connected with vinyl The accelerating agent of sub- substituent or the dosage of component can be more than 0.5%, or more than 1.0%, or more than 1.5%, or be more than 2.5%, or more than 3 weight %, and 20 weight % are less than, more preferably less than 15 weight %, or less than 10 weight %, or less than 5 Weight %, the weight % are relative to the weight mixed with the accelerating agent and the entire combination thing of component.
Light-initiated bag ratio
Inventor has found：The ratio of component relative to each other needed for if control is various, then according to the present invention group Compound can become to be directed to and be cured by using some addition process manufacturing process of UV/ visible light optical devices and especially be optimized. Therefore, in one embodiment, salt compounded of iodine cation light initiator and reducing agent, accelerating agent or with being connected with vinyl One or more molar ratios in the component of electron donating group are 2:1 to 1:50, more preferably 1:1 to 1:30, or 1:2 to 1: 20, or 1:5 to 1:10.
In one embodiment, Norrish I types photoinitiator and reducing agent, accelerating agent or with being connected with vinyl Electron donating group component in one or more molar ratios be 2:1 to 1:50, more preferably 1:1 to 1:30, or 1:2 to 1:20, or 1:5 to 1:10.
In one embodiment, salt compounded of iodine cation light initiator and the molar ratio of Norrish I type photoinitiators are 1:4 to 4:1, more preferably 1:2 to 2:1, or 3:4 to 4:3.
If the amount of salt compounded of iodine cation light initiator is too high, the incremental improvement of curing performance finally becomes to neglect Slightly, and value is less than increased cost, and the practicality with cost-benefit composition is prepared so as to hinder.If salt compounded of iodine The amount of cation light initiator is too low relative to other compositions, then cationic curing will not be initiated to required level to produce tool There are the three dimensional articles of enough green strengths.The amount of Norrish I type photoinitiators should not relative to the amount of cation light initiator The significant changes, but the amount of Norrish I type photoinitiators should be sufficient so that can carry out free redical polymerization component Direct polymerization and the cation light initiator indirect excitation.
The amount of accelerating agent or component with the electron donating group being connected with vinyl should be enough to promote sun from The cationic polymerization and/or related oxidized/reduction reaction that the free radical of sub-light initiator promotes.Finally, have and vinyl phase The accelerating agent or component of electron donating group even can be relative to the above-mentioned other compositions in light-initiated bag with maximum mole In the presence of, enable to fully carry out extra cationic polymerization mechanism, but in order to be made without prejudice to three-dimensional cure being made from it The mechanical performance of part, it should not be present in excess.
The component of cationically curable
According to a kind of embodiment, the liquid radiation curable resins for being used for addition process manufacture of the invention include at least one The component of kind cationically polymerizable, i.e. pass through the component that cation triggers or polymerize in the presence of raw sour agent.Can sun from The component of son polymerization can be monomer, oligomer and/or polymer, and can include aliphatic series, aromatics, alicyclic, aryl fat Race, heterocyclic fragments and its any combination.Preferably, the component of cationically polymerizable includes at least one alicyclic compound.Close Suitable cyclic ether compounds can include cyclic ethers base as side base or include that formation is alicyclic or the base of a part for heterocyclic ring system Group.
The component of cationically polymerizable is selected from by cyclic ether compounds, cyclic acetal compounds, cyclic thioether compounds, loop coil The group of ortho acid ester compounds, annular lactone compound and vinyl ether compound and its any combination composition.
The component of suitable cationically polymerizable includes cyclic ether compounds, such as epoxide and oxetanes；Ring Shape lactone compound；Cyclic acetal compounds；Cyclic thioether compounds；With spiro orthoester compound.Cationically polymerizable The specific example of component includes bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, bisphenol-S diglycidyl ether, bromination Bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ethers, brominated bisphenol S diglycidyl ethers, epoxy novolac tree Fat, hydrogenated bisphenol A diglycidyl ether, A Hydrogenated Bisphenol A F diglycidyl ethers, A Hydrogenated Bisphenol A S diglycidyl ethers, 3,4- epoxies Cyclohexyl methyl -3 ', 4 '-epoxycyclohexane carboxylate, 2- (3,4- epoxycyclohexyl -5,5- spiral shell -3,4- epoxy) hexamethylene -1, 4- dioxane, two (3,4- epoxycyclohexyl-methyl) adipate esters, vinylcyclohexene oxide, 4- vinyl epoxy hexamethylenes Alkane, vinyl cyclohexene dioxide, Yangization limonene, limonene dioxide, two (3,4- epoxy -6- methylcyclohexylmethyls) adipic acids Ester, 3,4- epoxy -6- methylcyclohexyls -3 ', 4 '-epoxy -6 '-methylcyclohexanecarboxylic acid ester, 3, the 4- rings that 6-caprolactone is modified Oxygen cyclohexyl methyl -3 ', 4 '-epoxycyclohexane carboxylate, 3, the 4- epoxycyclohexyl-methyls -3 ' of trimethyl caprolactone modification, 4 '-epoxycyclohexane carboxylate, 3, the 4- epoxycyclohexyl-methyls -3 ' that Beta-methyl-δ-valerolactone is modified, 4 ' -7-oxa-bicyclo[4.1.0 Carboxylate, di-2-ethylhexylphosphine oxide (3,4- 7-oxa-bicyclo[4.1.0), dicyclohexyl -3,3 '-epoxides, has connecting key-O-,-S-, - SO-,-SO2-,-C(CH3)2-,-CBr2-,-C(CBr3)2-,-C(CF3)2-,-C(CCl3)2-, or-CH (C6H5)-two (3,4- Epoxycyclohexyl), bicyclopentadiene diepoxide, two (3,4- epoxycyclohexyl-methyl) ethers of ethylene glycol, ethylene double (3,4- Epoxycyclohexane carboxylate), epoxy di-2-ethylhexyl hexahydrophthalate, two -2- ethylhexyls of epoxy hexahydro-phthalic acid Ester, 1,4-butanediol diglycidyl ether, 1,6- hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, glycerine three Glycidol ether, trihydroxymethylpropanyltri diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl Ether, the 2-glycidyl ester of long aliphatic chains binary acid, the monoglycidyl ether of aliphatic higher alcohol, phenol, cresols, butylphenol or The monoglycidyl ether of the Aethoxy Sklerol obtained by oxyalkylene and these compound additions, the glycidol of higher fatty acids Ester, epoxidised soybean oil, epoxybutyl stearate, epoxy octyl stearate, epoxidized linseed oil, epoxidation polybutadiene Alkene, Isosorbide-5-Nitrae-bis- [(3- ethyl -3- oxetanylmethoxies) methyl] benzene, 3- ethyl -3- hydroxymethyl-oxetanes, 3- second Base -3- (3- hydroxypropyls) oxygen methy oxetane, 3- ethyls -3- (4- hydroxyls butyl) oxygen methy oxetane, 3- ethyls -3- (5- hydroxyls amyl group) oxygen methy oxetane, 3- ethyl -3- phenoxymethyloxetanes, two (1- ethyls (3- oxa- ring fourths Alkyl) methyl) ether, 3- ethyls -3- ((2- ethyl hexyl oxies) methyl) oxetanes, 3- ethyls-((triethoxysilicane alkyl) Propoxy methyl) oxetanes, 3- (methyl) allyloxy methyl -3- Ethyloxetanes, 3- methylol -3- ethyl oxygen Azetidine, (3- ethyl -3- oxetanylmethoxies) methylbenzene, the fluoro- [1- (3- ethyl -3- oxetanyl first of 4- Epoxide) methyl] benzene, 4- methoxyl groups-[1- (3- ethyl -3- oxetanylmethoxies) methyl] benzene, [1- (3- ethyl -3- oxygen Azetidine ylmethoxy) ethyl] phenyl ether, isobutoxy methyl (3- ethyl -3- oxetanylmethyls) ether, 2- ethyl hexyls Base (3- ethyl -3- oxetanylmethyls) ether, ethyl diethylene glycol (3- ethyl -3- oxetanylmethyls) ether, two Cyclopentadiene (3- ethyl -3- oxetanylmethyls) ether, dicyclopentenyl oxygen ethyl (3- ethyl -3- oxetanyls Methyl) ether, dicyclopentenyl (3- ethyl -3- oxetanylmethyls) ether, tetrahydrofurfuryl (3- ethyl -3- oxetanes Ylmethyl) ether, 2- ethoxys (3- ethyl -3- oxetanylmethyls) ether, 2- hydroxypropyls (3- ethyl -3- oxetanes Ylmethyl) ether, and its any combination.
The component of cationically polymerizable optionally also includes multifunctional material, and the multifunctional material gathers including dendroid Compound, such as the polymerization of the amine dendrimer with epoxy or oxetane functionality, linear dendritic, dendrigfrat Thing, dissaving polymer, star-branched polymer and the polymer of super grafting.Dendritic can include a species Type polymerizable functional group or different types of polymerizable functional group, such as epoxy-functional and oxetane functionality.
In one embodiment, composition of the invention is also comprising aliphatic alcohol, aliphatic polyol, polyester polyol or poly- The one or more monoglycidyl ethers or polyglycidyl ether of ethoxylated polyhydric alcohol.The example of preferred ingredient includes 1,4- butanediols two Glycidol ether, molecular weight are the polyoxyethylene and the glycidol ether of polyoxypropylene diols and triol of about 200 to about 10000； Polytetramethylene glycol or the glycidol ether of poly- (ethylene oxide-oxygen butylene) random copolymer or block copolymer.Have in one kind In body embodiment, the component of cationically polymerizable, which is included in molecule, does not have the polyfunctional glycidyl ether of cyclohexane ring.Another In one embodiment, the component of cationically polymerizable includes neopentylglycol diglycidyl ether.In another specific embodiment party In formula, the component of cationically polymerizable includes 1,4-CHDM diglycidyl ether.
The example of commercially available preferably polyfunctional glycidyl ether has ErisysTM GE 22(ErisysTMProduct can be from Emerald Performance MaterialsTMObtain), HeloxyTM 48、HeloxyTM 67、HeloxyTM 68、 HeloxyTM 107(HeloxyTMModifying agent can be obtained from Momentive Specialty Chemicals) and F713.The example of commercially available preferably monofunctional glycidyl ether has HeloxyTM 71、HeloxyTM 505、HeloxyTM 7、 HeloxyTM8 and HeloxyTM 61。
In one embodiment, epoxides is 3,4- epoxycyclohexyl-methyls -3 ', 4 '-epoxycyclohexylcarboxylate (from the available CELLOXIDE of Daicel ChemicalTM2021P, or the CYRACURE obtained from Dow ChemicalTM UVR-6105), the bisphenol A-epichlorohydrin base epoxy of hydrogenation is (from the available EPON of MomentiveTM1510), Isosorbide-5-Nitrae-hexamethylene Alkane dimethanol diglycidyl ether is (from the available HELOXY of MomentiveTM107), hydrogenation bisphenol A diglycidyl ether (from The available EPON of MomentiveTM825), the mixture of bicyclohexane diepoxide and nano silicon dioxide (can conduct NANOPOXTMObtain) and their any combination.
In a detailed embodiment, the component of cationically polymerizable includes alicyclic epoxy, for example, according to the following formula Alicyclic epoxy with 2 or more than two epoxide group：
Wherein R is carbon atom, ester-containing C1-C10Aliphatic chain or C1-C10Alkyl chain.
In another embodiment, the component of cationically polymerizable is included with aromatics or aliphatic glycidyl ether The epoxy of group, it has 2 (difunctionalitys) or more than two (multifunctional) epoxide group.
The compound of above-mentioned cationically polymerizable can be used alone or two or more are applied in combination.The present invention's In embodiment, the component of cationically polymerizable also includes at least two different epoxy components.
In other embodiments of the present invention, the component of cationically polymerizable also includes oxetanes.One In a embodiment, the component of cationically polymerizable includes oxetanes, such as contains 1,2 or more than two oxygen The oxetanes of azetidine group.In another embodiment, oxetanes used is simple function, and in addition Also there is hydroxyl.According to a kind of embodiment, oxetanes has with lower structure：
If used in the composition, the suitable amount of oxetanes is about 5 weights of resin combination Measure % to about 50 weight %.In another embodiment, the amount of oxetanes is about 10 weights of resin combination Measure % to about 25 weight %；In yet another embodiment, the amount of oxetanes is 20 weights of resin combination Measure % to about 30 weight %.
Therefore, the liquid radiation curable resins for addition process manufacture can include proper amount of cationically polymerizable Component, such as in some embodiments, be resin combination about 10 weight % to about 80 weight %, in other embodiment party It is the about 20 weight % to about 70 weight % of resin combination in formula, is in other embodiment about the 25 of resin combination To about 65 weight %.
The component of free redical polymerization
A kind of embodiment according to the present invention, the liquid radiation curable resins bag for being used for addition process manufacture of the invention Component (that is, triggering the component to be polymerize by free radical) containing at least one free redical polymerization.Free redical polymerization Component be monomer, oligomer, and/or polymer；They are simple function or polyfunctional material, i.e. have 1,2,3,4,5, 6th, 7,8,9,10 ... 20 ... 30 ... 40 ... 50 ... 100 or more functional groups that can be triggered by free radical to polymerize, can wrap Fatty race, aromatic series, alicyclic, aromatic yl aliphat, heterocyclic fragments or its any combination.The example of multifunctional material includes Dendritic, such as amine dendrimer, linear dendritic, dendroid graft polymers, dissaving polymer, star Shape branched polymer and the polymer of super grafting；See, e.g., 2009/0093564 A1 of US.Dendritic can wrap Containing a type polymerizable functional group or different types of polymerizable functional group, such as acrylate and methacrylate function Group.
The example of the component of free redical polymerization includes acrylate and methacrylate, such as (methyl) acrylic acid is different Norbornene ester, (methyl) acrylic acid norbornene ester, (methyl) acrylic acid tricyclodecyl ester, (methyl) acrylic acid bicyclopentyl ester, (first Base) acrylic acid dicyclopentenyl base ester, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid 4- fourths Cyclohexyl acetate, acryloyl morpholine, (methyl) acrylic acid, (methyl) 2-hydroxyethyl acrylate, (methyl) acrylic acid 2- hydroxypropyls Base ester, (methyl) acrylic acid 2- hydroxyls butyl ester, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid third Ester, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, caprolactone acrylate, (methyl) isoamyl acrylate, (methyl) third The own ester of olefin(e) acid, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid 2- Ethylhexyl, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid It is tridecane base ester, (methyl) acrylic acid hendecane base ester, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, different hard Lipidol (methyl) acrylate, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid butoxyethyl acetate, (methyl) acrylic acid Ethoxydiglycol ester, (methyl) benzyl acrylate, (methyl) phenoxy ethyl acrylate, polyethyleneglycol (methyl) third Olefin(e) acid ester, polypropylene glycol list (methyl) acrylate, (methyl) methoxyethyl glycol ester, (methyl) ethioxy Ethyl ester, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, diacetone (methyl) third Acrylamide, (methyl) β-acryloxypropionic acid, phthalic acid (methyl) acrylate, (methyl) acrylate second Ester, (methyl) diethylaminoethyl acrylate, (methyl) acrylic acid Butylcarbamoyl ethyl ester, N- isopropyls (methyl) propylene (methyl) acrylate of acid amides fluorination, (methyl) acrylic acid 7- amino -3,7- dimethyl-octa base esters.
The example of the component of polyfunctional free redical polymerization includes those with (methyl) acryloyl group, such as three hydroxyls Methylpropane three (methyl) acrylate, pentaerythrite (methyl) acrylate, ethylene glycol two (methyl) acrylate, bisphenol-A Diglycidyl ether two (methyl) acrylate, bicyclopentadiene dimethanol two (methyl) acrylate, [2- [1,1- diformazans Base -2- [(1- oxos pi-allyl) oxygen] ethyl] -5- ethyl -1,3- dioxane -5- bases] methacrylate, the double (1,1- of 3,9- Dimethyl -2- ethoxys) two (methyl) acrylate of -2,4,8,10- four oxygen spiral shell [5.5] hendecane, dipentaerythritol monohydroxy Five (methyl) acrylate, propenoxylated trimethylolpropane tris (methyl) acrylate, propenoxylated neopentyl glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate, 1,6-HD two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, glycerine three (methyl) acrylate, mono phosphoric acid ester (methyl) propylene Acid esters and di(2-ethylhexyl)phosphate (methyl) acrylate, two (methyl) acrylate C7-C20Arrcostab, three (2- ethoxys) isocyanuric acids three (methyl) acrylate, three (2- ethoxys) isocyanuric acid two (methyl) acrylate, pentaerythrite three (methyl) acrylate, Pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tricyclic last of the ten Heavenly stems diyl dimethyl two (methyl) The alkoxylated variation (such as ethoxylation and/or propenoxylated) of acrylate and above any type monomer, also There are two (methyl) acrylate of the glycol of the adduct of ethylene oxide or propylene oxide and bisphenol-A, and ethylene oxide or ring Two (methyl) acrylate of the glycol of the adduct of Ethylene Oxide and hydrogenated bisphenol A, (it is bis-phenol to epoxy (methyl) acrylate The adduct of A diglycidyl ethers and (methyl) acrylate), the diacrylate of polyalkoxylated bisphenol-A, triethylene glycol Divinyl ether, the adduct of hydroxy ethyl methacrylate.
According to a kind of embodiment, the component of free redical polymerization is multifunctional (methyl) acrylate.Multifunctional (first Base) acrylate can include any group of full methylacryloyl, full acryloyl group or methylacryloyl and acryloyl group Close.In one embodiment, the combination of free redical polymerization is selected from consisting of the following group：Bisphenol A diglycidyl ether two (methyl) acrylate, ethoxylation or propenoxylated bisphenol-A or Bisphenol F two (methyl) acrylate, bicyclopentadiene two Methanol two (methyl) acrylate, [2- [1,1- dimethyl -2- [(1- oxos pi-allyl) oxygen] ethyl] -5- ethyl -1,3- Er Evil Alkane -5- bases] methacrylate, dipentaerythritol monohydroxy five (methyl) acrylate, dipentaerythritol five (methyl) propylene Acid esters, dipentaerythritol six (methyl) acrylate, propenoxylated trimethylolpropane tris (methyl) acrylate and the third oxygen (methyl) acrylate of neopentyl glycol two and its any combination of base.
In one embodiment, multifunctional (methyl) acrylate has more than two functional group.According to another real Mode is applied, multifunctional (methyl) acrylate, which has, is more than 3 functional groups.In another embodiment, multifunctional (methyl) Acrylate, which has, is more than 4 functional groups.In another preferred embodiment, the component of free redical polymerization exclusively by Single multifunctional (methyl) acrylate component composition.In other embodiment, the exclusive free redical gathers The component of conjunction is tetrafunctional；In other embodiment, the component of the exclusive free redical polymerization is five functions 's；In other embodiment, the component of the exclusive free redical polymerization is six functions.
In another embodiment, the component of free redical polymerization contains aromatics (methyl) acrylate.As unrestricted Property example, aromatic acrylic ester can be derived from bisphenol-A, bisphenol S or Bisphenol F.In some embodiments, aromatic acrylic ester Selected from consisting of the following group：Bisphenol A diglycidyl ether diacrylate, bicyclopentadiene Dimethanol Diacrylate, [2- [1,1- dimethyl -2- [(1- oxos pi-allyl) oxygen] ethyl] -5- ethyl -1,3- dioxane -5- bases] methacrylate, two Pentaerythrite monohydroxypentaacrylate, propenoxylated trimethylolpropane trimethacrylate and propenoxylated new penta 2 Alcohol diacrylate and its any combination.In one embodiment, aromatics (methyl) acrylate is difunctionality.
In some specific embodiments, the liquid radiation curable resins for being used for addition process manufacture of the invention include Bisphenol A diglycidyl ether two (methyl) acrylate, bicyclopentadiene dimethanol two (methyl) acrylate, dipentaerythritol Monohydroxy five (methyl) acrylate, propenoxylated trimethylolpropane tris (methyl) acrylate, and/or propenoxylated One or more in neopentyl glycol two (methyl) acrylate, more specifically comprising two propylene of bisphenol A diglycidyl ether Acid esters, bicyclopentadiene Dimethanol Diacrylate, Dipentaerythritol Pentaacrylate, propenoxylated trimethylolpropane tris One or more in acrylate and/or propenoxylated neopentylglycol diacrylate.
The compound of above-mentioned free redical polymerization can be used alone or two or more are applied in combination.For addition process The liquid radiation curable resins of manufacture can include the component of any proper amount of free redical polymerization, for example, in some realities Apply in mode, be the at most about 50 weight % of resin combination；In some embodiments, it is about 2 weights of resin combination Measure % to about 40 weight %；In other embodiments, it is the about 5 weight % to about 30 weight % of resin combination；In addition Embodiment in, be resin combination about 10 weight % to about 20 weight %.
Optional additive
Composition according to the present invention is optionally including one or more of additives.Usually using stabilizer as addition Agent is added in resin combination further to prevent viscosity from increasing, such as the viscosity during solid state image during use increases Add.Available stabilizer includes those described in United States Patent (USP) No.5,665,792.The presence of stabilizer is optional.One In a specific embodiment, the liquid radiation-curable resin composition for addition process manufacture includes 0.1 weight %-3 weights Measure the stabilizer of %.
Other possible additives include organic and inorganic filler, dyestuff, pigment, antioxidant, wetting agent, bubble collapse Agent, chain-transferring agent, levelling agent, defoamer, surfactant etc..This additive is known, and usually can be according to spy Surely used using desired, as understood by those skilled in the art.
The liquid radiation-curable resin composition for being used for addition process manufacture of the present invention can also include one or more Selected from consisting of the following group of additive：Bubble collapse agent, antioxidant, surfactant, plumper, pigment, dyestuff, increasing Thick dose, fire retardant, silane coupling agent, ultraviolet absorber, resin particle, core-shell particles impact modifier, soluble polymer and Block polymer.
In addition, many known liquid radiation-curable resin compositions for addition process manufacture use hydroxy-functional Compound strengthens the performance of the product made of the resin combination.It can be used for (if present) using any hydroxyl Specific purpose.If it exists, material containing hydroxy groups preferably comprise one or more primary aliphatic hydroxide radicals or secondary aliphatic hydroxide radical.Hydroxyl Can portion or end in the molecule.Monomer, oligomer or polymer can be used.Hydroxyl equivalent (i.e. number-average molecular weight divided by hydroxyl Radix) preferably in the range of 31-5000.It is if it exists, excellent relative to the gross weight of resin combination, resin combination Choosing includes at most 10 weight %, or at most 5 weight %, or the polymerizable hydroxyl of one or more non-free radicals of at most 2 weight % Base functional compound.
The third embodiment is to form three-dimensional system by using the addition process manufacture system of ultraviolet/visible light optics The method of product, the described method includes：
(1) provide any aspect of the first or second of embodiment according to the present invention is used for addition process manufacture Liquid radiation-hardenable composition；
(2) the first liquid level of liquid radiation curable resins is built；
(3) make the first liquid level Imagewise exposure in actinic radiation with shape by the configuration of ultraviolet/visible light optics Into imaging cross section, so as to form the first cured layer；
(4) mew layer of the liquid radiation curable resins contacted with first cured layer is formed；
(5) the mew layer Imagewise exposure is made in actinic radiation to form other imaging cross section；With
(6) repeat step (4) and (5) enough number are to build three-dimensional article；
Wherein described ultraviolet/visible light optics with about 375nm to about 500nm, more preferably from about 380nm to about 450nm, The peak value spectral intensity transmitting radiation of more preferably from about 390nm to about 425nm, more preferably from about 395nm to about 410nm.
The liquid radiation-hardenable composition provided in the third above-mentioned embodiment is suitable for by using UV/ visible rays The addition process manufacture system of optics is cured.Other places above describe this composition.Building the first liquid During the mew layer of layer or formation liquid radiation curable resins, layer can have any suitable thickness and shape, and depend on Used addition process manufacturing process.For example, layer can selectively be distributed by injection, or can be by by prior cured Layer immerse in resin barrel and be added, so as to produce the substantially homogeneous layer of thickness, this is to most of stereolithography works It is common for skill.In another non-limiting embodiment, layer can be alternatively via tubular article (cartridge) Or distributor is shifted with predetermined thickness via paper tinsel, film or carrier.
Hereinbefore, " exposure " refers to use actinic radiation.As it was previously stated, as described herein be used for what addition process manufactured The fluid radiation composition of the present invention to realize by ultraviolet/visible light optics especially suitable for mixing curing.In one kind In embodiment, LED is as light source for ultraviolet/visible light optics devices use one or more.In one embodiment, Light source is laser.In one embodiment, LED or laser light source are coupled to DLP or LCD image optical projection system.Wherein Image projection system is included in the embodiment of LCD display, and light source can be configured as only photochemical spoke of the transmitting higher than 400nm Penetrate, to minimize adverse effect of the UV wavelength to LCD element part.
4th kind of embodiment be using according to the first or second embodiment it is any for the use of radiation-hardenable The three-dimensional article that composition is formed by the third embodiment.
Following embodiments further illustrate the present invention, but are undoubtedly not necessarily to be construed as what is limit the invention in any way Scope.
Embodiment
These embodiments illustrate the embodiment of the liquid radiation curable resins for being used for addition process manufacture of the present invention. What is used in the embodiment that the invention has been described of table 1 is used for each component of the liquid radiation curable resins of addition process manufacture.
Table 1
The calculating of ionization potential
The program of this paper is used to obtain all ionization potential values.First, 14 software (Spartan ' of Spartan are utilized 14Version 1.1.2 on October 24th, 2013,1991-2013 returns Wavefunction Inc to own) structure sense The molecular structure of interest system.Using same program, conformational analysis is carried out using Merck molecular force fields (MMFF).Then use Semiempirical parametric method 6 (PM6) minimizes all MMFF conformations.
Optimize all unique conformations that operation produces as the export of .xyz coordinate files using by PM6, be then used as starting point with Using 09 programs of Gaussian (Gaussian 09, Revision C.01, M.J.Frisch, G.W.Trucks etc., Gaussian, Inc., Wallingford CT, 2010) quantum mechanics of higher level is carried out in B3LYP/6-31G (d) levels Calculate.Then the unrestricted wave function of spin of free radical and triplet is calculated.
Unrestricted B3LYP/6-31G (d) frequency is carried out after all optimization operations to calculate, it is obtained to determine Whether B3LYP/6-31G (d) structures are real energy-minimum in potential energy level.
Under the hypothesis of Koopmans theorems, ionization potential (IP) is obtained by the result of global minima conformation, i.e. by highest The energy of occupied molecular orbital (HOMO) obtains IP, such as P=- εHOMO, wherein HOMO energy is converted to electricity from a.u. (Hartree) Sub- volt (1Hartree=27.211383eV).Value is represented with electron-volt (eV).
According to this method calculate it is several known to Norrish I type photoinitiators triplet ionization potential such as following table Shown in 2.The ionization potential of the similar known free radical calculated is as shown in table 3 below.Finally, it is similar calculate have and vinyl phase The ionization potential of the various components of electron donating group even is as shown in table 4 below.
Table 2
The calculating triplet ionization potential (eV) of known photoinitiator/photosensitizer
Table 3
The calculating ionization potential (eV) of known free radical
Table 4
The calculating triplet ionization potential (eV) of various components with the electron donating group being connected with vinyl
Embodiment 1-60
First, the component listed according to method well known in the art by combining in table 5 below is prepared for addition legal system The matrix resin (" resin base 1 ") made, the component it includes cationically polymerizable (further include oxetanes, alicyclic Epoxides and diglycidyl ether epoxy), the component of free redical polymerization and chain-transferring agent additive.
Then according to rate of polymerization test method assessment resin base 1 described below when being closed with various light-initiated inclusions Curing performance under the conditions of ultraviolet/visible light.
Fig. 1 shows the master drawing of the curing performance of two kinds of compositions.Fig. 1 shows curing performance, by being used as the time The conversion % of the polymerizable components of function is represented.This conversion can be denoted as the cycloaliphatic epoxides of non-limiting example The polymerization amount of component, oxetanes or acrylate component.The data series of composition 1 are shown relative to composition The high conversion degree of 2 data series.Line 3 and 4 is shown：According to the program summarized herein, before the generation of every kind of composition The slope of the least square fitting line of three data points.It is worth noting that, the slope of line 3 (related to composition 1) is higher than The slope of line 4 (related to composition 2)；This shows faster initial conversion.Attempt in place of the point that vertical line 5 represents clearly The total conversion of measurement.For given composition, this, which is likely to be in material time, such as addition process manufacturing process, is necessary to be formed Another layer and must obtain certain convert so that composition effective for the time in the technique.It can be seen that：Composition 1 exists The conversion ratio shown at point 6 is significantly higher than conversion ratio of the composition 2 in same time point (at point 7).
Various curing rate parameters are reported, it is explained below and shows in table 6-9.Unless otherwise indicated, All values are listed with parts by weight.
Table 5
Resin base 1
Component formula Resin base 1
OXT-101 (3- ethyls -3- methylols-oxetanes) 10.5
UVR6105 ((3', 4'- 7-oxa-bicyclo[4.1.0) methyl 3,4- epoxycyclohexylcarboxylates) 36.8
PolyTHF-1000 (polytetramethylene glycol MW1000) 10.5
E828 (bisphenol A diglycidyl ether) 21.1
Ebecryl 3700 (bisphenol-A diglycidyl diacrylate) 21.1
Test method-rate of polymerization
In order to measure the rate of polymerization of each embodiment (curing rate), infrared (FTIR) light of real-time Fourier is used Spectroscopy.In order to improve data acquiring frequency and resolution ratio, mercury cadmium telluride (MCT) detector is used.(ATR) is totally reflected using decay Setting replaces transmission mode.The measurement of all rates of polymerization using 8700 patterns of Thermo Scientific Nicolet into OK.Following table shows the experiment condition setting for measurement.Under these conditions, every time measurement obtain totally 41 continue 200 The spectrum of second：
Scan number 4
Resolution ratio 4
Type of data collection In real time
Types of profiles Slope
Sequential Preserve 200 seconds
Use the repetition time (second) 5
Photocontrol for ultraviolet/visible light, uses digital light laboratory LED spotlights (400nm) and controller (AccuCure Photo Rheometer), and select " continuous mode of calibration ".Selection luminous intensity and duration before measurement (time for exposure).All embodiments all follow above-mentioned, and exception is embodiment 41-46 (table 7), wherein using 355nm solid-state lasers Device.
In order to measure, sample selected by several drops is placed in the center of atr crystal setting.Then, using 3mil (± 0.4mils) Spreading rod (draw down bird bar) the top coating about 3mil of atr crystal film (± 0.4mils).Coating After the coating of 3mil, LED light is maintained to the top of ATR settings immediately, and hole is placed on to the center of holding.Then start Real-time FTIR scannings.Once obtaining a spectrum in one (1), just open light source and start to polymerize.Inputted based on program above, every five seconds for example Clock obtains a spectrum, continues totally 200 seconds.Experiment obtains totally 41 spectrum every time.
Polymerization conversion and the relation of time are calculated based on the specific IR peak changes for representing each functional group.It is every in order to calculate The conversion ratio of a related functional group, optionally calculates peak heights or peak area according to following table (if applicable, from following table)：
Functional group Method Height or area (cm-1) Baseline (cm-1)
Cycloaliphatic epoxy resin Highly 787.791 856.253-778.149
Oxetanes Area 998.962-943.999 998.962-943.999
Acrylate Area 1419.374-1396.232 1419.374-1396.232
According to initial data, the LINEST letters in Microsoft Excel versions 14.0.7116.5000 (32) are used The least square method that number calculates the first three data point (terminating when ± 1 second 12 seconds) of cycloaliphatic epoxy resin polymerization conversion is intended Close, and be recorded in table 6 below -9 (be shown as " LSF " of 0-12 seconds).In addition, alicyclic epoxy, oxa- ring fourth when recording 200 seconds The polymerization conversion of alkane and/or acrylate and also it is reported in table 6-9 and (is optionally shown as " alicyclic epoxide at 200 seconds Thing conversion % ", " at 200 seconds acrylate conversion % " or " at 200 seconds oxetanes convert % ").
For the initial data of acquisition, in order to apply curing rate model, first to second data point is removed, because Opening FTIR detection devices and between the light source of solidified sample, testing curing rate program there is the unknown short time to prolong Late.In order to solve the relevant any uncertainty of statistical noise amount produced with these initial data points, for each data set Generate three groups of curve matchings.In each case, for the model equation for wanting fitting data collection be Conv=a (1-e (- b* (when It is m- c))).For this reason, it is fitted using the Microsoft Excel versions 14.0.7116.5000 (32) that attached data is analyzed Initial data.
In the first scenario, whole data set (including the first two data point) is fitted.In the latter case, entirely Data set subtracts first data point and is fitted.In a third case, whole data set subtracts first and second data Point is fitted.In each case, curve matching coefficient r is created2.Selection uses first number with higher than 1% conversion ratio Strong point and the combination of its curve matching produce the r higher than 0.902Data set, and the Fitting curve equation result of gained is used for Curing rate when further calculating platform conversion ratio is 95%.If curve matching coefficient r2Less than 0.90, then again again Run data.
As described above, data are synthesized to equation form Conv=a (1-e (- b* (when m- c))), wherein " Conv " is logical The conversion ratio % of FTIR peak ratios measurement is crossed, the time is the length of exposure, and " a " is platform conversion ratio, and " b " is to be used to calculate The obtained derived curing rate coefficient of curing rate, " c " are obtained derived curing induction times.Data are intended After conjunction, software can generate experimentally derived equation, wherein the numerical parameter of " a ", " b " and " c " be by experimental data and What fitting determined.For the material (i.e. epoxy and oxetanes) of cationically curable, " c " is nonsensical, because not solid Change induction time.However, for the integrality of model, these values are still reported herein.Variable " a " is used as condition of cure used Under platform conversion ratio, it represents total asymptotic degree for being converted of component.Variable " b " is used by equation T95=ln (.05/ B) the 95% platform conversion ratio (T of " a " is reached to calculate95) time.The T of variable " a ", " b " and " c " and each sample95Depending on Situation (if applicable) enters in table 6,7,8 and 9.
Table 6
Influence of the various light-initiated bags to curing performance under ultraviolet/visible light condition (400nm LED)
Table 7
Influence of the various light-initiated solvents to curing performance under UV conditions (355nm)
* the oxetanes conversion % when value of embodiment 41-43 represents 200 seconds, this is because lacking alicyclic epoxy Compound converts the authentic data of %.
Table 8
Influence of the various light-initiated solvents to curing performance under ultraviolet/visible light condition (400nm LED)
Table 9
Curing performance under ultraviolet/visible light condition (400nm LED)
Discussion of results
It can be seen that：When using light-initiated bag according to the present invention, it is obtained mix-polymerisable compound passing through Suitable cure for using the various addition processes of ultraviolet/visible light optics is shown during by ultraviolet/visible light condition In manufacturing process, the curing is by curve matching T95Value, conversion rate of epoxide, epoxides inversion quantity and/or propylene Acid esters inversion quantity measures.
Other illustrative embodiments
The present invention the first other illustrative embodiments first aspect be it is a kind of for addition process manufacture can spoke Solidification composition filling is penetrated, the composition includes：
(a) light-initiated bag, it includes
Salt cation photoinitiator；
Norrish I type photoinitiators；With
Optionally, the photosensitizer for salt cation photoinitiator described in photosensitizer；
(b) component of cationically curable, it includes
Optionally, cycloaliphatic epoxides；
Optionally, glycidyl ether epoxides, and
Optionally, oxetanes；
(c) component of free redical polymerization；
(d) there is the component for the electron donating group being connected with vinyl；With
(e) optionally, one or more additives.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the cation light initiator is salt compounded of iodine cationic photopolymerization Initiator.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein cycloaliphatic epoxides, glycidyl ether epoxides It is not optional with least one of oxetanes.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein cycloaliphatic epoxides, glycidyl ether epoxides It is not optional with least two in oxetanes.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein cycloaliphatic epoxides, glycidyl ether epoxides It is not optional with oxetanes.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the group with the electron donating group being connected with vinyl Point amount be 0.5 weight % to 20 weight %, or 1.0 weight % to 15 weight %, or 1.5 weight % to 10 weight %, Or 2.5 weight % to 8 weight %, or 3 weight % to 5 weight %.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I type photoinitiators are configured as By exposed to actinic radiation to excite when enter triplet, wherein the triplet of the excitation have be less than about 4.15eV, more It is preferred that 3.98eV, more preferably less than 3.90eV, more preferably less than 3.80eV, more preferably less than 3.70eV, more preferably less than The ionization potential of 3.55eV, wherein according to molecular model combination Koopman theorems (the IP=- ε under B3LYP/6-31G (d)HOMO) Calculate the ionization potential.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I type photoinitiators are configured as By exposed to actinic radiation to excite when enter triplet, wherein the triplet of the excitation has at least 2.5eV, more preferably At least ionization potential of 3.0eV, wherein according to the molecular model combination Koopman theorems (IP=- under B3LYP/6-31G (d) εHOMO) calculate the ionization potential.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I types photoinitiator is still used for light It is sensitized the photosensitizer of salt compounded of iodine cation light initiator.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention Aspect be used for addition process manufacture radiation-hardenable composition, wherein the Norrish I type photoinitiators be alkyl-, virtue Base-or acyl group-substituted.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein alkyl-, the Norrish I of aryl-or acyl group-substituted Type photoinitiator, which includes, has the 14th race's atom or the compound centered on the 14th race's atom.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein alkyl-, the Norrish I of aryl-or acyl group-substituted Type photoinitiator includes the compound with the atom selected from silicon, germanium, tin and lead.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein being that Norrish I types photoinitiator is acyl group germanium chemical combination Thing.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the acyl group germanium compound is with (I) according to the following formula Structure：
Wherein Ar1It is aromatic group, its is unsubstituted or is further taken by one or more following groups in any position Generation：Alkyl diradical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, by one Or the aromatic group or heterocyclic group or alkyl diradical that multiple ethers, thioether, silylation, carboxyl or vinyl interrupt, and Wherein R1、R2And R3Acyl group, aryl, alkyl or carbonyl can independently be, its it is unsubstituted or by one or more following groups into One step substitutes：Alkyl diradical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, The aromatic group or heterocyclic group or alkyl interrupted by one or more ethers, thioether, silylation, carboxyl or vinyl is free Base.
The another aspect of first illustrative embodiments is the foregoing aspect of the first illustrative embodiments according to the present invention Be used for addition process manufacture radiation-hardenable composition, wherein R1-R3In be each aryl substitution or aromatic acyl group； Or work as R1-R3In to have two be aryl substitution or during aromatic acyl group, remaining substituent is C1-C10, more preferably C1-C6, it is more excellent Select C1-C3Alkyl；Or work as R1-R3In to have one be aryl substitution or during aromatic acyl group, other two substituent is C1-C10、 More preferably C1-C6, more preferably C1-C3Alkyl；Or R1-R3In be each C1-C10, more preferably C1-C6, more preferably C1-C3Alkane Base.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the acyl group germanium compound is to be selected from following chemical combination Thing：
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I type photoinitiators are configured as Free radical is formed during exposed to actinic radiation.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein is formed by the Norrish I type photoinitiators oneself Had by base and be less than or equal to 5.50eV, more preferably less than the ionization potential of 5.00eV, the more preferably less than calculating of 4.80eV, institute It is by molecular model combination Koopman theorems (the IP=- ε under B3LYP/6-31G (d) to state ionization potentialHOMO) come what is calculated.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein is formed by the Norrish I type photoinitiators oneself There is the ionization potential of at least calculating of 4.05eV by base, the ionization potential is by the molecule mould under B3LYP/6-31G (d) Type combination Koopman theorems (IP=- εHOMO) come what is calculated.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein salt compounded of iodine cation light initiator and has and vinyl The molar ratio of the component of connected electron donating group is 2:1 to 1:50, more preferably 1:1 to 1:30, or 1:2 to 1:20, or 1:5 To 1:10.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein Norrish I types photoinitiator and has and vinyl The molar ratio of the component of connected electron donating group is 2:1 to 1:50, more preferably 1:1 to 1:30, or 1:2 to 1:20, or 1:5 To 1:10.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein salt compounded of iodine cation light initiator and Norrish I types The molar ratio of photoinitiator is 1:4 to 4:1, more preferably 1:2 to 2:1, or 3:4 to 4:3.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein relative to the gross weight of the photoinitiator bag, it is described Photoinitiator includes following material：
The salt compounded of iodine cation light initiator of 25 weight % to 33 weight %；
The Norrish I type photoinitiators of 10 weight % to 25 weight %；
The electron donating group being connected with vinyl of 33 weight % to 66 weight %.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the group with the electron donating group being connected with vinyl Divide to be configured as producing having and be less than or equal to 6.58eV, more preferably less than 5.42eV, less than 4.89eV, is more preferably less than The Vinyl radical of 4.30eV, the more preferably less than ionization potential of 4.20eV, wherein according to point under B3LYP/6-31G (d) Submodel combination Koopman theorems (IP=- εHOMO) calculate the ionization potential.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the group with the electron donating group being connected with vinyl Divide to be configured as producing and there is at least 3.3eV, the vinyl of the ionization potential of more preferably at least 3.5eV, more preferably at least 3.8eV Free radical, wherein according to molecular model combination Koopman theorems (the IP=- ε under B3LYP/6-31G (d)HOMO) described to calculate Ionization potential.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I type photoinitiators are configured as producing Free radical as life, the free radical have greater than about 104M-1s-1, more preferably greater than about 105M-1s-1, most preferably greater than about 3 ×105M-1s-1Add to the speed with the component of electron donating group being connected with vinyl.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the group with the electron donating group being connected with vinyl It is liquid to divide at 25 DEG C.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I types photoinitiator predissolve is existed In the solvent be made of the component with the electron donating group being connected with vinyl.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the group with the electron donating group being connected with vinyl Vinyl ethers, vinyl esters, vinyl sulfide, n- vinyl carbazoles, n- vinyl pyrrolidones, n- vinyl are selected from oneself Acid amides, allyl ether and vinylcarbonates.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the group with the electron donating group being connected with vinyl It is polyfunctional to divide.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the group with the electron donating group being connected with vinyl It is vinyl ethers to divide.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the photosensitizer is not optional and has excitation yet Triplet.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, is less than about wherein the excited triplet state of the photosensitizer has 4.15eV, more preferably less than about 3.98eV, more preferably less than 3.90eV, more preferably less than 3.80eV, more preferably less than 3.70eV, The more preferably less than ionization potential of 3.55eV, wherein according to the molecular model combination Koopman theorems under B3LYP/6-31G (d) (IP=- εHOMO) calculate the ionization potential.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the excited triplet state of the photosensitizer has greater than about The ionization potential of 2.5eV, more preferably at least about 3.0eV, wherein being combined according to the molecular model under B3LYP/6-31G (d) Koopman theorems (IP=- εHOMO) calculate the ionization potential.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the ionization potential of the excited triplet state of the photosensitizer is big In the ionization potential of the excited triplet state of Norrish I type photoinitiators.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein light-initiated relative to entire combination thing, Norrish I types The amount (by weight) of agent in the composition is higher than the amount (by weight) of photosensitizer in the composition.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein oxetanes are simple function and in addition have hydroxyl Base.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the cycloaliphatic epoxides component has according to the following formula Structure：
Wherein R is carbon atom or ester-containing C1-C10Aliphatic chain.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the diglycidyl ether epoxy is selected from based on bisphenol-A Glycidol ether, the glycidol ether based on bisphenol S and the glycidol ether based on Bisphenol F.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the salt compounded of iodine cation light initiator is diphenyl iodine Salt.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the diphenyl iodnium is selected from (4- aminomethyl phenyls) [4- (2- methyl-propyls) phenyl]-, hexafluorophosphate, [4- (1- Methylethyls) phenyl] (4- aminomethyl phenyls)-, four (phenyl-pentafluorides Base) borate (1-), (double (4- dodecylphenyls) iodine hexafluorophosphates) and (double (4- tert-butyl-phenyls) iodine hexafluoro phosphorus Hydrochlorate).
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, if wherein the radiation-hardenable composition is exposed to transmitting The ultraviolet/visible light optics of following radiation 10 seconds, the radiation have the output of peak value spectrum at 400nm, and in institute The surface for stating radiation-hardenable composition has 2mW/cm2Irradiation level, can realize：
Cycloaliphatic epoxides at 200 seconds are converted at least about 60%, and more preferably at least about 65%, more preferably at least about 70%.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein when the radiation-hardenable composition is under transmitting When stating the ultraviolet/visible light optics 10 seconds of radiation, the radiation 400nm at there is peak value spectrum to export, and in institute The surface for stating radiation-hardenable composition has 2mW/cm2Irradiation level, can realize：
Cycloaliphatic epoxides T95Value is less than about 100 seconds, more preferably less than about 90 seconds, more preferably less than about 80 seconds, more excellent Choosing is less than about 70 seconds, more preferably less than about 60 seconds.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein when the radiation-hardenable composition is under transmitting When stating the ultraviolet/visible light optics 10 seconds of radiation, the radiation 400nm at there is peak value spectrum to export, and in institute The surface for stating radiation-hardenable composition has 2mW/cm2Irradiation level, can realize：
The least square fitting of the cycloaliphatic epoxides conversion ratio of initial 12 seconds is at least about 1.25s-1, more preferably extremely Few about 1.65s-1, more preferably at least about 2.00s-1。
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein when the radiation-hardenable composition is under transmitting When stating the ultraviolet/visible light optics 10 seconds of radiation, the radiation 400nm at there is peak value spectrum to export, and in institute The surface for stating radiation-hardenable composition has 2mW/cm2Irradiation level, can realize：
Acrylate conversion at 200 seconds is at least about 95%, more preferably from about 100%.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the light-initiated bag is substantially by following material composition：
A kind of salt compounded of iodine cation light initiator；
A kind of Norrish I type photoinitiators with excited triplet state；
A kind of photosensitizer；With
A kind of component with the electron donating group being connected with vinyl.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the light-initiated bag is substantially by following material composition：
A kind of salt compounded of iodine cation light initiator；
A kind of Norrish I type photoinitiators with excited triplet state；With
A kind of component with the electron donating group being connected with vinyl.
The another aspect of first illustrative embodiments is any foregoing of the first illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the composition is substantially by following material composition：
Light-initiated bag any one of two preceding claims；
A kind of cycloaliphatic epoxides component；
A kind of glycidyl ether epoxides component；
A kind of oxetanes；With
One or more polymerizable compounds.
The first aspect of the second other illustrative embodiments of the present invention is that the liquid manufactured for addition process can spoke Solidification composition filling is penetrated, the composition includes：
Light-initiated bag, it includes
Salt cation photoinitiator；
Reducing agent, it includes
A effective amount of Norrish I type photoinitiators, it is dissolved in
For in the vinyl ether compound of liquid at 25 DEG C；With
Optionally, photosensitizer；
The component of cationically polymerizable；
The component of free redical polymerization；With
Optionally, one or more additives.
The another aspect of second illustrative embodiments is the foregoing aspect of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture, wherein to be dissolved in inertia dilute for the salt cation photoinitiator Release in agent.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the inert diluent includes propylene carbonate.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I types photoinitiator being capable of shape Ionization potential into calculating is less than or equal to 5.50eV, more preferably less than the free radical of 5.00eV, more preferably less than 4.80eV, institute The ionization potential for stating calculating is by molecular model combination Koopman theorems (the IP=- ε under B3LYP/6-31G (d)HOMO) come Calculate.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I types photoinitiator being capable of shape Ionization potential into calculating is at least free radical of 4.05eV.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I types photoinitiator can be into Enter triplet, wherein the triplet, which has, is less than about 4.15eV, more preferably less than about 3.98eV, more preferably less than 3.90eV, The ionization potential of more preferably less than 3.80eV, more preferably less than 3.70eV, more preferably less than 3.55eV, wherein according to B3LYP/6- Molecular model combination Koopman theorems (IP=- ε under 31G (d)HOMO) calculate the ionization potential.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I types photoinitiator can be into Enter triplet, wherein the triplet has at least 2.5eV, the more preferably at least ionization potential of 3.0eV, wherein according to B3LYP/ Molecular model combination Koopman theorems (IP=- ε under 6-31G (d)HOMO) calculate the ionization potential.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein relative to entire combination thing, the Norrish I The amount (by weight) of type photoinitiator is 0.1 weight % to about 10 weight %, more preferably from about 0.3 weight % to about 5 weights Measure %, more preferably from about 0.5 weight % to about 3 weight %.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the reducing agent can produce such freedom Base, the free radical, which has, is less than or equal to 6.58eV, and more preferably less than 5.42eV, less than 4.89eV, is more preferably less than The calculating ionization potential of 4.30eV, more preferably less than 4.20eV, wherein being combined according to the molecular model under B3LYP/6-31G (d) Koopman theorems (IP=- εHOMO) calculate the ionization potential.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the reducing agent can produce such freedom Base, the free radical, which has, is less than or equal to 6.58eV, and more preferably less than 5.42eV, less than 4.89eV, is more preferably less than The calculating ionization potential of 4.30eV, more preferably less than 4.20eV, wherein being combined according to the molecular model under B3LYP/6-31G (d) Koopman theorems (IP=- εHOMO) calculate the ionization potential.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein can be by the Norrish I type photoinitiators The free radical of formation has greater than about 104M-1s-1, more preferably greater than about 105M-1s-1, most preferably greater than about 3 × 105M-1s-1Plus Into the speed to vinyl ethers.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I type light of free radical can be formed Initiator be alkyl-, aryl-or acyl group-substitution.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid radiation-hardenable composition, wherein the free radical formed be used for go back crude salt sun from The reducing agent of sub-light initiator.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I types photoinitiator is substantially It is made of such compound, the compound, which has, is selected from the 14th race's element, is preferably selected from the atom of silicon, germanium, tin and lead.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the Norrish I types photoinitiator is substantially It is made of acyl group germanium compound.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the acyl group germanium compound is substantially by following formula (I) the compound composition represented by：
Wherein Ar1It is aromatic group, its is unsubstituted or is further taken by one or more following groups in any position Generation：Alkyl diradical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, by one Or the aromatic group or heterocyclic group that multiple ethers, thioether, silylation, carboxyl or vinyl interrupt, or alkyl diradical, and Wherein R1、R2And R3Acyl group, aryl, alkyl or carbonyl can independently be, its it is unsubstituted or by one or more following groups into One step substitutes：Alkyl diradical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, The aromatic group or heterocyclic group interrupted by one or more ethers, thioether, silylation, carboxyl or vinyl, or alkyl are free Base.
The another aspect of second illustrative embodiments is the foregoing aspect of the second illustrative embodiments according to the present invention Be used for addition process manufacture liquid radiation-hardenable composition, wherein R1-R3In be each aryl substitution or aromatics acyl Base；Or work as R1-R3In to have two be aryl substitution or during aromatic acyl group, remaining substituent is C1-C10, more preferably C1-C6、 More preferably C1-C3Alkyl；Or work as R1-R3In to have one be aryl substitution or during aromatic acyl group, other two substituent is C1- C10, more preferably C1-C6, more preferably C1-C3Alkyl；Or R1-R3In be each C1-C10, more preferably C1-C6, more preferably C1- C3Alkyl.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid radiation-hardenable composition, wherein the acyl group germanium compound substantially by with appoint A kind of compound composition of following molecular structure：
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein relative to the weight of entire combination thing, the second The amount of alkenyl ether compound is 0.5 weight % to 20 weight %, or 1.0 weight % to 15 weight %, or 1.5 weight % are extremely 10 weight %, or 2.5 weight % to 8 weight %, or 3 weight %% to 5 weight %.
The another aspect of second illustrative embodiments is the foregoing aspect of the second illustrative embodiments according to the present invention Be used for addition process manufacture liquid radiation-hardenable composition, wherein relative to the weight of entire combination thing, the vinyl The amount of ether compound is less than 15 weight %, more preferably less than 10 weight %, more preferably less than 5 weight %.
The another aspect of first illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein salt cation photoinitiator and reducing agent rub You are than being 1:1 to 1:50, more preferably 3:4 to 1:20, or 1:2 to 1:15, or 1:3 to 1:8.
The another aspect of first illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid radiation-hardenable composition, wherein the reducing agent of Norrish I types photoinitiator with The molar ratio of vinyl ether compound is 1:1 to 1:50, more preferably 2:3 to 1:30, or 1:2 to 1:20, or 1:5 to 1: 10。
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the vinyl ether compound includes triethylene glycol Divinyl ether.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the component of the cationically curable includes：
Cycloaliphatic epoxides；
Glycidyl ether epoxides；With
Oxetanes.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein oxetanes are simple functions and in addition have There is hydroxyl.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the cycloaliphatic epoxides are substantially by 3,4- Epoxycyclohexyl-methyl -3', 4'- epoxycyclohexane carboxylate form.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the glycidyl ether epoxides component is selected from Glycidol ether based on bisphenol-A, the glycidol ether based on bisphenol S and the glycidol ether based on Bisphenol F.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the component of the cationically curable is substantially not Containing vinyl ether compound.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the light-initiated bag is substantially by following material group Into：
A kind of salt cation photoinitiator；
A kind of reducing agent, it is with a kind of Norrish I type photoinitiators, the Norrish I types photoinitiator dissolving For in the vinyl ether compound of liquid at a kind of 25 DEG C；With
Optionally, photosensitizer.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein the composition is substantially by following material group Into：
Light-initiated bag described in preceding claims；
A kind of cycloaliphatic epoxides component；
A kind of glycidyl ether epoxides component；
A kind of oxetanes；With
One or more polymerizable compounds.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein when the liquid radiation-hardenable composition exposes When the ultraviolet/visible light optics 10 seconds of following radiation is launched, the radiation 400nm at there is peak value spectrum to export, And there is 2mW/cm on the surface of the liquid radiation-hardenable composition2Irradiation level, can realize：
Cycloaliphatic epoxides T95Value is less than about 100 seconds, more preferably less than about 90 seconds, more preferably less than about 80 seconds, more excellent Choosing is less than about 70 seconds, more preferably less than about 60 seconds.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein when the liquid radiation-hardenable composition exposes When the ultraviolet/visible light optics 10 seconds of following radiation is launched, the radiation 400nm at there is peak value spectrum to export, And there is 2mW/cm on the surface of the liquid radiation-hardenable composition2Irradiation level, can realize：
Cycloaliphatic epoxides at 200 seconds are converted at least about 60%, and more preferably at least about 65%, more preferably at least about 70%.
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein when the liquid radiation-hardenable composition exposes When the ultraviolet/visible light optics 10 seconds of following radiation is launched, the radiation 400nm at there is peak value spectrum to export, And the liquid can the surface of ultraviolet/visible light radiation-curable composition there is 2mW/cm2Irradiation level, can realize：
The least square fitting of the cycloaliphatic epoxides conversion ratio of initial 12 seconds is at least about 1.25s-1, more preferably extremely Few about 1.65s-1, more preferably at least about 2.00s-1。
The another aspect of second illustrative embodiments is any foregoing of the second illustrative embodiments according to the present invention The liquid radiation-hardenable composition for being used for addition process manufacture of aspect, wherein when the liquid radiation-hardenable composition exposes When the ultraviolet/visible light optics 10 seconds of following radiation is launched, the radiation 400nm at there is peak value spectrum to export, And the liquid can the surface of ultraviolet/visible light radiation-curable composition there is 2mW/cm2Irradiation level, can realize：
Acrylate conversion at 200 seconds is at least about 95%, more preferably from about 100%.
The first aspect of 3rd other illustrative embodiments of the invention be for addition process manufacture liquid can it is ultraviolet/ Visible radiation solidification composition filling, the composition include：
(a) light-initiated bag, it includes：
The salt compounded of iodine cation light initiator of 0.1 weight % to 15 weight %；
The Norrish I type photoinitiators of 0.1 weight % to 5 weight %；
From more than 0.5%, preferably greater than 1.0%, preferably greater than 1.5%, preferably greater than 2.5%, preferably greater than 3% to 20%, more preferably 15%, more preferably 10%, more preferably 5%, to less than 20 weight %, is more preferably less than 15 weight %, more preferably Less than the accelerating agent of 10 weight %；
(b) component of cationically curable, it includes：
The oxetanes of 1 weight % to 20 weight %；
The cycloaliphatic epoxides of 3 weight % to 40 weight %；With
The glycidyl ether epoxides of 2 weight % to 40 weight %；
(c) 5 weight % to the free redical polymerization of about 40 weight % component；With
(d) optionally, at most one or more additives of 50 weight %；
Wherein all wt percentage is listed both with respect to the weight of entire combination thing.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention The liquid for being used for addition process manufacture of aspect can ultraviolet/visible light radiation-curable composition, wherein accelerating agent contains vinyl.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein when the liquid is radiation-curable solid When changing composition exposed to the ultraviolet/visible light optics 10 seconds for launching following radiation, the radiation has peak at 400nm Be worth spectrum output, and the liquid can the surface of ultraviolet/visible light radiation-curable composition there is 2mW/cm2Irradiation Degree, can realize：
Cycloaliphatic epoxides T95Value is less than about 100 seconds, more preferably less than about 90 seconds, more preferably less than about 80 seconds, more excellent Choosing is less than about 70 seconds, more preferably less than about 60 seconds.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein when the liquid is radiation-curable solid When changing composition exposed to the ultraviolet/visible light optics 10 seconds for launching following radiation, the radiation has peak at 400nm Be worth spectrum output, and the liquid can the surface of ultraviolet/visible light radiation-curable composition there is 2mW/cm2Irradiation Degree, can realize：
Cycloaliphatic epoxides at 200 seconds are converted at least about 60%, and more preferably at least about 65%, more preferably at least about 70%.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein when the liquid is radiation-curable solid When changing composition exposed to the ultraviolet/visible light optics 10 seconds for launching following radiation, the radiation has peak at 400nm Be worth spectrum output, and the liquid can the surface of ultraviolet/visible light radiation-curable composition there is 2mW/cm2Irradiation Degree, can realize：
The least square fitting of the cycloaliphatic epoxides conversion ratio of initial 12 seconds is at least about 1.25s-1, more preferably extremely Few about 1.65s-1, more preferably at least about 2.00s-1。
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein when the liquid is radiation-curable solid When changing composition exposed to the ultraviolet/visible light optics 10 seconds for launching following radiation, the radiation has peak at 400nm Be worth spectrum output, and the liquid can the surface of ultraviolet/visible light radiation-curable composition there is 2mW/cm2Irradiation Degree, can realize：
Acrylate conversion at 200 seconds is at least about 95%, more preferably from about 100%.
The another aspect of first illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein mole of salt compounded of iodine cation light initiator and accelerating agent Than for 2:1 to 1:50, more preferably 1:1 to 1:30, or 1:2 to 1:20, or 1:5 to 1:10.
The another aspect of first illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein mole of Norrish I types photoinitiator and accelerating agent Than for 2:1 to 1:50, more preferably 1:1 to 1:30, or 1:2 to 1:20, or 1:5 to 1:10.
The another aspect of first illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention The radiation-hardenable composition for being used for addition process manufacture of aspect, wherein salt compounded of iodine cation light initiator and Norrish I types The molar ratio of photoinitiator is 1:4 to 4:1, more preferably 1:2 to 2:1, or 3:4 to 4:3.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein the accelerating agent is vinyl Ether compound.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, it also includes photosensitizer, for controlling The penetration depth of resin.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention The liquid for being used for addition process manufacture of aspect can ultraviolet/visible light radiation-curable composition, wherein for controlling resin penetration deep The photosensitizer of degree has no substantial effect on the curing rate of resin.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein the salt compounded of iodine is selected from (4- first Base phenyl) [4- (2- methyl-propyls) phenyl]-, hexafluorophosphate, [4- (1- Methylethyls) phenyl] (4- aminomethyl phenyls)-, four (pentafluorophenyl group) borate (1-), (double (4- dodecylphenyls) iodine hexafluorophosphates) and (double (4- tert-butyl-phenyls) iodine Hexafluorophosphate).
The another aspect of first illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture radiation-hardenable composition, wherein the Norrish I types photoinitiator for alkyl-, virtue Base-or acyl group-substituted and include the compound with the atom from the 14th race's element.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein the Norrish I type light draws Hair agent for alkyl-, aryl-or acyl group-substituted and include the compound with the atom selected from silicon, germanium, tin and lead.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention The liquid for being used for addition process manufacture of aspect can ultraviolet/visible light radiation-curable composition, wherein alkyl-, aryl-or acyl group- Substituted Norrish I type photoinitiators are acyl group germanium compounds.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein relative in the composition The gross weight of existing all Norrish I type photoinitiators, the Norrish I types photoinitiator include at least 80 weights Measure formula (I) under %, more preferably at least 90 weight %, more preferably at least 94 weight %, the most preferably at least satisfaction of 97 weight % Acyl group germanium compound：
Wherein Ar1It is aromatic group, its is unsubstituted or is further taken by one or more following groups in any position Generation：Alkyl diradical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, by one Or the aromatic group or heterocyclic group that multiple ethers, thioether, silylation, carboxyl or vinyl interrupt, or alkyl diradical, and Wherein R1、R2And R3Acyl group, aryl, alkyl or carbonyl can independently be, its it is unsubstituted or by one or more following groups into One step substitutes：Alkyl diradical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, The aromatic group or heterocyclic group interrupted by one or more ethers, thioether, silylation, carboxyl or vinyl, or alkyl are free Base.
The another aspect of 3rd illustrative embodiments is the foregoing aspect of the 3rd illustrative embodiments according to the present invention Be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein R1-R3In be each that aryl takes Generation or aromatic acyl group；Or work as R1-R3In to have two be aryl substitution or during aromatic acyl group, remaining substituent is C1-C10、 More preferably C1-C6, more preferably C1-C3Alkyl；Or work as R1-R3In to have one be aryl substitution or during aromatic acyl group, remaining two A substituent is C1-C10, more preferably C1-C6, more preferably C1-C3Alkyl；Or R1-R3In be each C1-C10, more preferably C1-C6, more preferably C1-C3Alkyl.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein relative in the composition The gross weight of existing all acyl group germanium compounds, the acyl group germanium compound include at least 80%, more preferably at least 90 weights Measure %, most preferably at least more preferably at least 94 weight %, one or both of following compound of 97 weight %：
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein the accelerating agent can be formed Based on vinyl or ether free radical, wherein it is described had based on vinyl or ether free radical be less than or equal to 6.58eV, more preferably Less than 5.42eV, less than the calculating ionization potential of 4.89eV, more preferably less than 4.30eV, more preferably less than 4.20eV, wherein root According to molecular model combination Koopman theorems (the IP=- ε under B3LYP/6-31G (d)HOMO) calculate the ionization potential.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein the Norrish I type light draws Hair agent is configured as producing such free radical, and the free radical, which has, is more than 104, more preferably greater than 105, most preferably greater than or Equal to 3 × 106The speed for adding to vinyl ethers.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein relative in entire combination thing The weight of existing all Norrish I type photoinitiators, the composition include at least 50%, more preferably at least 60%, more Preferably at least 80%, more preferably at least 90%, the more preferably at least 95% Norrish I type light with potential excited triplet state Initiator, wherein the ionization potential of the potential excited triplet state is less than 4.15eV or less than 3.98eV or less than 3.90eV or small In 3.80eV or less than 3.70eV or less than 3.55eV, wherein being combined according to the molecular model under B3LYP/6-31G (d) Koopman theorems (IP=- εHOMO) calculate the ionization potential.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein relative in entire combination thing The weight of existing all Norrish I type photoinitiators, the composition include at least 50%, more preferably at least 60%, more Preferably at least 80%, more preferably at least 90%, the more preferably at least 95% Norrish I type light with potential excited triplet state Initiator, wherein the ionization potential of the potential excited triplet state is at least 2.5eV, more preferably at least 3.0eV, wherein basis Molecular model combination Koopman theorems (IP=- ε under B3LYP/6-31G (d)HOMO) calculate the ionization potential.
The another aspect of 3rd illustrative embodiments is any foregoing of the 3rd illustrative embodiments according to the present invention Aspect be used for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, wherein relative in entire combination thing The weight of existing all Norrish I type photoinitiators, the composition include at least 50%, more preferably at least 60%, more Preferably at least 80%, more preferably at least 90%, the more preferably at least 95% Norrish I type light with potential derivative free radical Initiator, the calculating ionization potential of the potential derivative free radical are less than or equal to 5.50eV, more preferably less than 5.00eV, more excellent Choosing is less than 4.80eV, wherein according to molecular model combination Koopman theorems (the IP=- ε under B3LYP/6-31G (d)HOMO) calculate The ionization potential.
The present invention the 4th additional example embodiment first aspect be for addition process manufacture liquid it is radiation-curable Solidification composition filling, relative to the weight of entire combination thing, it includes：
0.1 weight % to 15 weight %, or 0.5 weight % to about 10 weight %, or 1 weight % is to 8 weight %, or 2 weights Measure the salt compounded of iodine cation light initiator of % to 5 weight %；
0.05 weight % to 15 weight %, or 0.1 weight % to 10 weight %, or 0.5 weight % is to 8 weight %, or 1 weight Measure the compound of (I) according to the following formula of % to 5 weight %：
Wherein Ar1It is aromatic group, its is unsubstituted or is further taken by one or more following groups in any position Generation：Alkyl diradical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, by one Or the aromatic group or heterocyclic group that multiple ethers, thioether, silylation, carboxyl or vinyl interrupt, or alkyl diradical, and Wherein R1、R2And R3Acyl group, aryl, alkyl or carbonyl can independently be, its it is unsubstituted or by one or more following groups into One step substitutes：Alkyl diradical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, The aromatic group or heterocyclic group interrupted by one or more ethers, thioether, silylation, carboxyl or vinyl, or alkyl are free Base；
0.5 weight % to 20 weight %, or 1.0 weight % to 20 weight %, or 1.5 weight % are to 15 weight %, or 2 weights Measure % to 15 weight %, or 2.5 weight % to 15 weight %, or 2.5 weight % to 10 weight %, or the ethene of about 3 weight % Base ether；
Optionally, 3 weight % to 30 weight %, or 3 weight % to 25 weight %, or 5 weight % are to the oxygen of 20 weight % Azetidine；
Optionally, 1 weight % to 45 weight %, or 3 weight % to 35 weight %, or 5 weight % are to the fat of 25 weight % Ring race epoxides；
2 weight % to 50 weight %, or 3 weight % to 40 weight %, or 5 weight % are to the glycidol ether of 30 weight % Epoxides；
5 weight % to about 60 weight %, or 10 weight % to about 50 weight %, or 15 weight % to 40 weight % can from By base polymeric component；With
Optionally, at most one or more additives of 50 weight %.
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What it is foregoing aspects of for addition process manufacture liquid radiation-hardenable composition, wherein when according to the compound of formula (I) by light When changing radiation fully excitation and forming excited triplet state, if combined according to the molecular model under B3LYP/6-31G (d) Koopman theorems (IP=- εHOMO) calculating ionization potential, then the excited triplet state is shown less than 4.15eV, more preferably small In 3.98eV, more preferably less than 3.90eV, more preferably less than 3.80eV, more preferably less than 3.70eV, more preferably less than 3.55eV Ionization potential.
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What it is foregoing aspects of for addition process manufacture liquid radiation-hardenable composition, wherein when according to the compound of formula (I) by light When changing radiation fully excitation and forming excited triplet state, if combined according to the molecular model under B3LYP/6-31G (d) Koopman theorems (IP=- εHOMO) calculating ionization potential, then the excited triplet state shows at least 2.5eV, more preferably at least The ionization potential of 3.0eV.
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What foregoing aspects of liquid radiation-hardenable composition for addition process manufacture, if wherein according under B3LYP/6-31G (d) Molecular model combination Koopman theorems (IP=- εHOMO) calculate ionization potential, then it can be formed according to the compound of formula (I) Calculate ionization potential and be less than or equal to 5.50eV, more preferably less than the free radical of 5.00eV, more preferably less than 4.80eV.
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What foregoing aspects of liquid radiation-hardenable composition for addition process manufacture, if wherein according under B3LYP/6-31G (d) Molecular model combination Koopman theorems (IP=- εHOMO) calculate ionization potential, then it can be formed according to the compound of formula (I) Calculate the free radical that ionization potential is more than 4.05eV.
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What foregoing aspects of liquid radiation-hardenable composition for addition process manufacture, it further includes 0.01 weight % to about 10 Weight %, more preferably 0.25 weight % are to about 5 weight %, the chloro- 4- propoxyl group of 1- of more preferably from about 0.5 weight % to 3 weight % Thioxanthones or 9,10- diethoxy anthracenes.
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What foregoing aspects of liquid radiation-hardenable composition for addition process manufacture, wherein the cycloaliphatic epoxides and oxa- Cyclobutane is not optional.
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What foregoing aspects of liquid radiation-hardenable composition for addition process manufacture, if wherein according under B3LYP/6-31G (d) Molecular model combination Koopman theorems (IP=- εHOMO) calculating ionization potential, then vinyl ethers can produce calculating ionization electricity Gesture is less than or equal to 6.58eV, more preferably less than 5.42eV, less than 4.89eV, more preferably less than 4.30eV, is more preferably less than 4.20eV free radical.
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What foregoing aspects of liquid radiation-hardenable composition for addition process manufacture, wherein can be produced according to the compound of formula (I) Free radical as life, the free radical, which has, is greater than or equal to 104M-1s-1, more preferably or equal to about 105M-1s-1, most preferably Greater than or equal to about 3 × 105M-1s-1The speed for adding to vinyl ether components.
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What it is foregoing aspects of for addition process manufacture liquid radiation-hardenable composition, wherein the additive be not it is optional and Include filler or polyalcohol.
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What foregoing aspects of liquid radiation-hardenable composition for addition process manufacture, wherein when the liquid radiation-hardenable combines When thing is exposed to the ultraviolet/visible light optics 10 seconds for launching following radiation, the radiation has peak value spectrum at 400nm Output, and the liquid can the surface of ultraviolet/visible light radiation-curable composition there is 2mW/cm2Irradiation level, can Realize：
Cycloaliphatic epoxides T95Value is less than about 100 seconds, more preferably less than about 90 seconds, more preferably less than about 80 seconds, more excellent Choosing is less than about 70 seconds, more preferably less than about 60 seconds.
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What foregoing aspects of liquid radiation-hardenable composition for addition process manufacture, wherein when the liquid radiation-hardenable combines When thing is exposed to the ultraviolet/visible light optics 10 seconds for launching following radiation, the radiation has peak value spectrum at 400nm Output, and the liquid can the surface of ultraviolet/visible light radiation-curable composition there is 2mW/cm2Irradiation level, can Realize：
Cycloaliphatic epoxides at 200 seconds are converted at least about 60%, and more preferably at least about 65%, more preferably at least about 70%.
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What foregoing aspects of liquid radiation-hardenable composition for addition process manufacture, wherein when the liquid radiation-hardenable combines When thing is exposed to the ultraviolet/visible light optics 10 seconds for launching following radiation, the radiation has peak value spectrum at 400nm Output, and the liquid can the surface of ultraviolet/visible light radiation-curable composition there is 2mW/cm2Irradiation level, can Realize：
The least square fitting of the cycloaliphatic epoxides conversion ratio of initial 12 seconds is at least about 1.25s-1, more preferably extremely Few about 1.65s-1, more preferably at least about 2.00s-1。
The another aspect of 4th illustrative embodiments of the invention is times of the 4th illustrative embodiments according to the present invention What foregoing aspects of liquid radiation-hardenable composition for addition process manufacture, wherein when the liquid radiation-hardenable combines When thing is exposed to the ultraviolet/visible light optics 10 seconds for launching following radiation, the radiation has peak value spectrum at 400nm Output, and the liquid can the surface of ultraviolet/visible light radiation-curable composition there is 2mW/cm2Irradiation level, can Realize：
Acrylate conversion at 200 seconds is at least about 95%, more preferably from about 100%.
The first aspect of the 5th additional exemplary embodiment of the present invention is by using ultraviolet/visible light optics The method that addition process manufacture system forms three-dimensional article, the described method includes：
(1) liquid for being used for addition process manufacture described in any foregoing aspect of any foregoing exemplary embodiment is provided Radiation-hardenable composition；
(2) the first liquid level of liquid radiation curable resins is built；
(3) make the first liquid level Imagewise exposure in actinic radiation with shape by the configuration of ultraviolet/visible light optics Into imaging cross section, so as to form the first cured layer；
(4) mew layer of the liquid radiation curable resins contacted with first cured layer is formed；
(5) the mew layer Imagewise exposure is made in actinic radiation to form other imaging cross section；With
(6) repeat step (4) and (5) enough number are to build three-dimensional article；
Wherein described ultraviolet/visible light optics with about 375nm to about 500nm, more preferably from about 380nm to about 450nm, The peak value spectral intensity transmitting radiation of more preferably from about 390nm to about 425nm, more preferably from about 395nm to about 410nm.
The another aspect of the 5th illustrative embodiments of the present invention is the foregoing of the 5th illustrative embodiments of the invention The method that the addition process manufacture system by using ultraviolet/visible light optics described in aspect forms three-dimensional article, wherein The ultraviolet/visible light optical arrangement is selected from LED/DLP, laser/DLP, LED/LCD and one kind or more in laser/LCD Kind.
The another aspect of the 5th illustrative embodiments of the present invention is by the 5th illustrative embodiments of the invention The three dimensional articles that method described in any foregoing aspect is formed, wherein first to fourth illustrative embodiments using the present invention Any one of any aspect described in liquid radiation-hardenable composition.
Unless otherwise indicated, term weight % refers to that special component is used for the complete of addition process manufacture relative to what it was mixed The amount (in mass) of portion's liquid radiation-hardenable composition.
Unless otherwise indicated herein, or otherwise clearly contradicted, describing in the context of the present invention (especially will in right In the context for seeking book) term that uses " one/a kind of ", " described " and limit and be appreciated that both without using numeral-classifier compound Include plural number again including odd number.Unless otherwise stated, term " comprising ", " having ", "comprising" and " containing " are understood to open Term (means " including, but are not limited to ").Unless otherwise indicated herein, the narration of number range herein is solely for the model Interior each stenography method being individually worth is enclosed, and each individually value is included in specification, just as they are individually listed in It is the same in specification.All methods as described herein can carry out in any suitable order, unless otherwise indicated herein, It is or otherwise clearly contradicted.Unless otherwise specified, provided herein is any and all example, or exemplary language (example Such as, " such as ") only it is used for preferably illustrating the present invention, rather than invention scope is any limitation as.Any sentence is not in specification It should be interpreted：Key element necessary for representing the implementation to the present invention, not being claimed.
There is described herein the preferred embodiment of the present invention, it includes, and inventor is known to be used for implementing the optimal of the present invention Mode.Certainly, on the basis of aforementioned specification is read, to the change in these preferred embodiments for the common skill in this area It will be apparent for art personnel.The present inventor contemplates those skilled in the art and suitably uses such change, and And inventor be expected the present invention can be to be implemented except otherwise than as specifically described herein.Therefore, as long as being applicable in Law allows, and the present invention includes all changes and the equivalent carried out to the theme mentioned in appended claims.It is in addition, all In possible change, any combinations of key element above-mentioned are all included in the present invention, unless otherwise indicated herein, or with it is upper It is hereafter clearly contradicted.
Although the present invention above is described in detail with reference to embodiment, it will be understood by those skilled in the art that right These embodiments carry out various changes and modification and will be apparent without departing from the spirit and scope of the present invention.

Claims (30)

1. it is a kind of for addition process manufacture can ultraviolet/visible light radiation-curable composition, the composition includes：
Light-initiated bag, it includes：
The salt compounded of iodine cation light initiator of about 0.1 weight % to about 15 weight %；
The Norrish I type photoinitiators of about 0.1 weight % to about 8 weight %；
The accelerating agent of about 0.1 weight % to about 15 weight %；With
Optionally, photosensitizer；
The component of cationically curable, it includes：
The oxetanes of about 1 weight % to about 20 weight %；
The cycloaliphatic epoxides of about 3 weight % to about 40 weight %；With
The glycidyl ether epoxides of about 2 weight % to about 40 weight %；
About 5 weight % to the free-radical curable of about 40 weight % component；With
Optionally, at most about one or more additives of 50 weight %；
Wherein described Norrish I type photoinitiators are the compounds of alkyl, aryl or acyl group-substituted, its have selected from silicon, The atom of germanium, tin and lead；And
Wherein all wt percentage is listed both with respect to the weight of entire combination thing.
2. it is according to claim 1 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein described Accelerating agent includes the electron donating group being connected with vinyl.
3. it is according to claim 2 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein described The molar ratio of salt compounded of iodine cation light initiator and the accelerating agent is 1:2 to 1:20,
The molar ratio of the Norrish I types photoinitiator and the accelerating agent is 1:2 to 1:20, and
The molar ratio of the salt compounded of iodine cation light initiator and the Norrish I type photoinitiators is 1:2 to 2:1.
4. it is according to claim 3 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein described The electron donating group being connected with vinyl is selected from vinyl ethers, vinyl esters, vinyl sulfide, n- vinyl carbazoles, n- second One or more in vinyl pyrrolidone, n- caprolactams, allyl ether and vinylcarbonates.
5. it is according to claim 4 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein described Accelerating agent is polyfunctional vinyl ether compound.
6. it is according to claim 5 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein described Salt compounded of iodine be selected from (4- aminomethyl phenyls) [4- (2- methyl-propyls) phenyl]-, hexafluorophosphate, [4- (1- Methylethyls) phenyl] (4- aminomethyl phenyls)-, four (pentafluorophenyl group) borates (1-) are (double (4- dodecylphenyls) iodine hexafluorophosphates) and (double (4- tert-butyl-phenyls) iodine hexafluorophosphate).
7. it is according to claim 4 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein described Norrish I types photoinitiator includes the compound for meeting lower formula (I)：
Wherein Ar1It is aromatic group, its is unsubstituted or is further substituted with any position by one or more following groups：Alkane Base free radical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, by one or more The aromatic group or heterocyclic group that a ether, thioether, silylation, carboxyl or vinyl interrupt, or alkyl diradical, and wherein R1、R2And R3Acyl group, aryl, alkyl or carbonyl can independently be, its is unsubstituted or further by one or more following groups Substitution：Alkyl diradical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, by one The aromatic group or heterocyclic group that a or multiple ethers, thioether, silylation, carboxyl or vinyl interrupt, or alkyl diradical.
8. it is according to claim 7 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein meeting One of the following conditions：
(a)R1-R3In be each aryl substitution or aromatic acyl group；Or
If (b) R1-R3In have two be aryl substitution or aromatic acyl group, then remaining substituent is C1-C10Alkyl；Or
If (c) R1-R3In have one be aryl substitution or aromatic acyl group, then other two substituent is C1-C10Alkyl；Or Person
(d)R1-R3In be each C1-C10Alkyl.
9. it is according to claim 4 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein relatively The gross weight of all Norrish I type photoinitiators present in the composition, the Norrish I types photoinitiator bag Containing at least one or both of following compound of 80 weight %：
10. it is according to claim 2 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein institute Stating accelerating agent can form based on vinyl or ether free radical, wherein being combined when according to the molecular model under B3LYP/6-31G (d) Koopman theorems (IP=- εHOMO) when calculating ionization potential, it is described that about 3.3eV is had to about based on vinyl or ether free radical The calculating ionization potential of 4.89eV.
11. it is according to claim 10 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein when According to molecular model combination Koopman theorems (the IP=- ε under B3LYP/6-31G (d)HOMO) calculate ionization potential when, the base In the calculating ionization potential of vinyl or ether free radical be about 3.80eV to about 4.20eV.
12. it is according to claim 4 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein institute State Norrish I type photoinitiators to be configured as producing such free radical, the free radical, which has, is greater than or equal to 3 × 106M-1s-1The speed for adding to the vinyl ethers.
13. it is according to claim 11 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein phase For the weight of all Norrish I type photoinitiators present in entire combination thing, the composition includes at least 80 weights The Norrish I type photoinitiators with potential excited triplet state of % are measured, if wherein according under B3LYP/6-31G (d) Molecular model combination Koopman theorems (IP=- εHOMO) calculate ionization potential, the then potential excited triplet state ionization potential It is about 3.0eV to about 3.98eV.
14. it is according to claim 5 for addition process manufacture can ultraviolet/visible light radiation-curable composition, wherein phase For entire combination thing, the amount of the polyfunctional vinyl ether compound by weight is about 1.5 weight % to about 8 weights Measure %.
15. a kind of liquid for addition process manufacture can ultraviolet/visible light radiation-curable composition, the composition includes：
Light-initiated bag, it includes
Salt cation photoinitiator；
Reducing agent, it includes
A effective amount of Norrish I type photoinitiators, it is dissolved in
For in the vinyl ether compound of liquid at 25 DEG C；With
Optionally, photosensitizer；
The component of cationically polymerizable；
The component of free redical polymerization；With
Optionally, one or more additives；
Wherein described Norrish I type photoinitiators be configured as by exposed to actinic radiation to excite when enter it is triple State, wherein the triplet of the excitation has the ionization potential of about 2.5eV to about 4.15eV, wherein according to B3LYP/6-31G (d) Under molecular model combination Koopman theorems (IP=- εHOMO) calculate the ionization potential.
16. it is according to claim 15 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its Described in the excited triplet states of Norrish I type photoinitiators there is the ionization potential of about 3.0e V to about 3.55eV, wherein root According to molecular model combination Koopman theorems (the IP=- ε under B3LYP/6-31G (d)HOMO) calculate the ionization potential.
17. it is according to claim 16 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its Described in salt cation photoinitiator be salt compounded of iodine cation light initiator.
18. it is according to claim 17 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its Described in Norrish I type photoinitiators be configured as forming following free radical, the free radical when exposed to actinic radiation With the calculating ionization potential less than 5.00eV, wherein being determined by the molecular model combination Koopman under B3LYP/6-31G (d) Manage (IP=- εHOMO) calculate the ionization potential.
19. it is according to claim 18 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its Described in Norrish I type photoinitiators be configured as forming following free radical, the free radical when exposed to actinic radiation Calculating ionization potential with about 4.05eV to about 4.80eV, wherein being combined by the molecular model under B3LYP/6-31G (d) Koopman theorems (IP=- εHOMO) calculate the ionization potential.
20. it is according to claim 19 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its Described in Norrish I type photoinitiators be configured as producing such free radical, the free radical has greater than about 105M-1s-1 The speed for adding to the vinyl ether compound.
21. it is according to claim 17 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its Described in the component of cationically polymerizable include cycloaliphatic epoxides, glycidol ether and oxetanes.
22. it is according to claim 21 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its In relative to entire combination thing weight, the amount of the vinyl ethers is 0.5 weight % to 20 weight %.
23. it is according to claim 22 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its In relative to entire combination thing weight, the amount of the vinyl ethers is 2 weight % to 8 weight %.
24. it is according to claim 23 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its Described in Norrish I types photoinitiator still be used for salt compounded of iodine cation light initiator described in photosensitizer photosensitizer.
25. it is according to claim 23 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its Described in Norrish I types photoinitiator include alkyl-, the compound of aryl-or acyl group-substituted, wherein the alkyl-, virtue Base-or acyl group-substituted compound also have the atom selected from silicon, germanium, tin and lead.
26. it is according to claim 25 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its Described in Norrish I types photoinitiator include acyl group germanium compound.
27. it is according to claim 26 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its Described in acyl group germanium compound there is the structure of (I) according to the following formula：
Wherein Ar1It is aromatic group, its is unsubstituted or is further substituted with any position by one or more following groups：Alkane Base free radical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, by one or more The aromatic group or heterocyclic group that a ether, thioether, silylation, carboxyl or vinyl interrupt, or alkyl diradical, and wherein R1、R2And R3Acyl group, aryl, alkyl or carbonyl can independently be, its is unsubstituted or further by one or more following groups Substitution：Alkyl diradical, ether, thioether, silylation, halogen, carboxyl, vinyl, aromatic group or heterocyclic group in addition, by one The aromatic group or heterocyclic group that a or multiple ethers, thioether, silylation, carboxyl or vinyl interrupt, or alkyl diradical.
28. it is according to claim 23 for addition process manufacture liquid can ultraviolet/visible light radiation-curable composition, its In when the radiation-hardenable composition is exposed to the ultraviolet/visible light optics 10 seconds for launching following radiation, the spoke Penetrating at 400nm has the output of peak value spectrum, and has 2mW/cm on the surface of the radiation-hardenable composition2Irradiation Degree, the radiation-hardenable composition are realized：
Cycloaliphatic epoxides at 200 seconds are converted at least about 65%,
The least square fitting of the cycloaliphatic epoxides conversion ratio of initial 12 seconds is at least about 1.25s-1, and
Acrylate conversion at 200 seconds is at least about 95%.
29. a kind of method that addition process manufacture system by using ultraviolet/visible light optics forms three-dimensional article, described Method includes：
(1) providing the liquid according to claim 21 for addition process manufacture can ultraviolet/visible light radiation-curable composition Thing；
(2) the first liquid level of the liquid radiation curable resins is built；
(3) the first liquid level Imagewise exposure is made in actinic radiation by the configuration of ultraviolet/visible light optics to be formed into As cross section, so as to form the first cured layer；
(4) formed the liquid that is contacted with first cured layer can ultraviolet/visible light radiation curing resin mew layer；
(5) the mew layer Imagewise exposure is made in actinic radiation to form other imaging cross section；With
(6) repeat step (4) and (5) enough number are to build three-dimensional article；
Wherein described ultraviolet/visible light optics launches radiation with the peak value spectral intensity of about 375nm to about 435nm.
30. according to the method for claim 29, wherein the ultraviolet/visible light optical arrangement is selected from LED/DLP, laser One or more in device/DLP, LED/LCD and laser/LCD.
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